WO2014126215A1

WO2014126215A1 - Graft copolymer, thermoplastic resin composition, and moulded article of said resin composition

Info

Publication number: WO2014126215A1
Application number: PCT/JP2014/053518
Authority: WO
Inventors: 幸作垰; 梨沙仁位; 吉昭篠原; 長谷　信隆
Original assignee: ユーエムジー・エービーエス株式会社; 三菱レイヨン株式会社
Priority date: 2013-02-15
Filing date: 2014-02-14
Publication date: 2014-08-21
Also published as: US20150376395A1; PT2957580T; CN105008420B; EP2957580B8; EP2957580A4; US9657169B2; EP2957580A1; CA2897935A1; MX2015010432A; CA2897935C; EP2957580B1; CN105008420A; PL2957580T3; HUE046407T2; ES2746798T3

Abstract

This graft copolymer is obtained by polymerizing a vinyl monomer mixture (m1) including an aromatic vinyl compound and a vinyl cyanide compound, in the presence of: an ethylene/α-olefin copolymer (A) which has a mass average molecular weight (Mw) in the range of 17×10⁴ to 35×10⁴, and a molecular weight distribution (Mw/Mn) in the range of 1-3; or a crosslinked ethylene/α-olefin copolymer (C) obtained by crosslinking the ethylene/α-olefin copolymer (A).

Description

Graft copolymer, thermoplastic resin composition and molded article thereof

The present invention relates to a thermoplastic resin composition and a molded product thereof.
The present application was filed on February 15, 2013 in Japanese Patent Application No. 2013-028360 filed in Japan, February 15, 2013, Japanese Patent Application No. 2013-028361 filed in Japan, on February 15, 2013. Japanese Patent Application No. 2013-028362 filed in Japan, Japanese Patent Application No. 2013-028130 filed in Japan on February 15, 2013, Japanese Patent Application No. 2014-2014 filed in Japan on February 3, 2014 The priority is claimed based on Japanese Patent Application No. 2014-018865 filed in Japan on February 3, 2014, and the contents thereof are incorporated herein.

Vehicle exterior parts such as door mirrors, pillars, bumpers, front grills, cowls and the like have high impact resistance and good appearance, so the materials include ABS resin, ASA resin, polymethyl methacrylate, High appearance quality was obtained by coating a molded article of thermoplastic resin such as polycarbonate.

In recent years, since the burden on the environment is large, the process is complicated, and the defect rate is high, a coloring agent may be blended in advance with a thermoplastic resin, and the coating treatment of the molded product may be omitted.
When coating treatment is omitted, high weather resistance is required for thermoplastic resins, so ethylene / propylene / non-conjugated diene copolymer, acrylic ester rubber, hydrogenated butadiene rubber with good weather resistance as rubber AES resin, ASA resin and the like having good weather resistance using hydrogenated rubber such as silicone rubber and the like are used.

However, if the surface of the molded product is damaged during the manufacturing or processing of the molded product or for a long period of time, the design properties are significantly reduced. Therefore, improvement in scratch resistance is desired depending on the application. .
Therefore, in order to improve the scratch resistance of the molded product, the surface of the molded product is reduced by reducing the amount of rubber to harden the molded product surface (see Patent Document 1) or by adding a lubricant such as silicone oil or olefin wax. (See Patent Document 2), adding a layered clay mineral intercalated with an organic compound to a rubber-modified thermoplastic resin (see Patent Document 3), or a specific range of acrylics in ABS resin, etc. A method of blending a specific amount of a methyl methacrylate-methyl acrylate copolymer containing methyl acid (see Patent Document 4) has been proposed.

However, in the method of reducing the amount of rubber as described in Patent Document 1, the surface hardness of the molded product is increased, so that the scratch resistance against scratches is improved, but the impact strength is reduced, so that the impact resistance and scratch resistance are reduced. There is a limit to achieving compatibility.
As described in Patent Document 2, the method of adding a lubricant such as silicone oil or olefin wax improves the slipperiness of the surface of the molded article, but is insufficient in improving the scratch resistance.
Moreover, since additives such as silicone oil bleed out on the surface of the molded product, glossiness and color developability may be impaired.
In the method of adding a special additive to the thermoplastic resin as described in Patent Document 3, the compatibility with the thermoplastic resin is often insufficient, and the appearance is poor such as a decrease in glossiness and color developability. In addition, the impact resistance may decrease.
In the method of blending a special resin with ABS resin or the like as described in Patent Document 4, there is an effect of improving the scratch resistance against scratches caused when a molded article surface is scratched with a hard object such as a nail. The scratch resistance against scratches generated when the surface of a molded product is rubbed with a soft material such as gauze or cloth is insufficient.
In addition, thermoplastic resins are also required to have excellent fluidity during molding, but the techniques described in the above-mentioned patent documents are not always satisfactory.

Improving the impact resistance of the molded product not only expands the applications of the molded product, but also makes it extremely useful for industrial applications, such as enabling the molded product to be made thinner and larger. . Therefore, various techniques have been proposed so far for improving the impact resistance of the molded product.
Among these methods, by using a resin material in which a rubber polymer and a hard resin are combined, a method for improving the impact resistance of a molded product while maintaining the characteristics derived from the hard resin has already been industrialized. . Examples of such resin materials include acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-styrene-acrylic acid ester (ASA) resin, acrylonitrile-ethylene / propylene / non-conjugated diene copolymer-styrene (AES) resin, or Examples thereof include a thermoplastic resin composition obtained by further adding these to a hard resin.

In addition, when a high design property is required for a molded product, a coating product is applied to the molded product obtained from these resin materials to obtain a high appearance quality. However, the painting process has problems such as a large environmental load, complicated processes, and a high defect rate. For this reason, a coloring agent may be blended in advance with the resin material, and the coating treatment of the molded product may be omitted. When coating treatment is omitted, high weather resistance is required for the molded product. Therefore, resin materials that can obtain molded products with good weather resistance, such as ethylene / propylene / non-conjugated diene as a rubbery polymer. AES resin, ASA resin, or the like using a polymer, acrylic ester rubber, hydrogenated rubber (hydrogenated butadiene rubber or the like), silicone rubber or the like is used.

However, a molded product that uses a resin material that can obtain a molded product with good weather resistance and that does not require a coating process is used during manufacturing of the molded product, during processing of the molded product, while the molded product is used for a long time, etc. When the surface of the molded product is damaged, the designability is remarkably lowered. Therefore, improvement of scratch resistance is desired depending on the application of the molded product. Then, in order to improve the scratch resistance of a molded article, it has been proposed to use the following thermoplastic resin composition.

(1) A rubbery material comprising a graft copolymer obtained by polymerizing a vinyl monomer mixture containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of a rubber polymer, and a hard resin. The surface of the molded product is hardened using a thermoplastic resin composition having a low polymer ratio (see Patent Document 1).
(2) A lubricant (polyolefin wax, silicone oil) is added to a graft copolymer obtained by polymerizing a vinyl monomer mixture containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of a rubber polymer. Etc.) is used to improve the slipperiness of the surface of the molded product (see Patent Document 2).
(3) A layered clay obtained by intercalating an organic compound with a graft copolymer obtained by polymerizing a vinyl monomer mixture containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of a rubbery polymer. A thermoplastic resin composition containing a mineral is used (see Patent Document 3).
(4) A graft copolymer obtained by polymerizing a vinyl monomer mixture containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of a rubbery polymer, and an aromatic vinyl compound and a vinyl cyanide compound A thermoplastic resin composition comprising a copolymer obtained by polymerizing a vinyl-based monomer mixture containing styrene and a copolymer obtained by copolymerizing methyl methacrylate and methyl acrylate in a specific ratio (See Patent Document 4).

When the thermoplastic resin composition (1) is used, the hardness of the surface of the molded product is increased, so that the scratch resistance against scratches is improved, but the ratio of the rubbery polymer is decreased, so that Impact strength decreases. Therefore, there is a limit to satisfy both the impact resistance and the scratch resistance of the molded product.
When the thermoplastic resin composition (2) is used, although the slipperiness of the surface of the molded product is improved, the improvement of scratch resistance is insufficient. Further, since the lubricant bleeds out on the surface of the molded product, the glossiness and color developability may be impaired.
In the thermoplastic resin composition of (3), the compatibility between the graft copolymer and the layered clay mineral intercalated with an organic compound is often insufficient. As a result, the appearance of the molded product may be poor (such as a decrease in glossiness or color developability) or impact resistance may be reduced.
(4) When the thermoplastic resin composition is used, the scratch resistance of the molded product against scratches is improved, but the scratch resistance of the molded product against scratches is insufficient.
The thermoplastic resin composition is also required to have excellent fluidity at the time of molding, but the fluidity of the thermoplastic resin composition (1) to (4) is not always satisfactory.

For example, the following thermoplastic resin compositions are known as thermoplastic resin compositions capable of obtaining molded articles having improved impact resistance while retaining the properties derived from the hard resin.
(1) A thermoplastic resin composition in which an AES resin is added to a hard resin and the ratio of the rubbery polymer is lowered to harden the surface of the molded product (Patent Document 1).
(2) A thermoplastic resin composition obtained by adding an AES resin to a methacrylic ester resin which is a hard resin (Patent Document 5).
(3) A thermoplastic resin composition in which an AES resin is added to a maleimide copolymer that is a hard resin (Patent Document 6).
(4) A thermoplastic resin composition obtained by adding an AES resin and an ASA resin to a methacrylic ester resin which is a hard resin (Patent Document 7).

When the thermoplastic resin composition (1) is used, the hardness of the surface of the molded product is increased, so that the scratch resistance against scratches is improved, but the ratio of the rubbery polymer is decreased, so that Impact strength decreases.
Therefore, there is a limit to satisfy both the impact resistance and the scratch resistance of the molded product.
In the thermoplastic resin compositions of (2) and (3), it is necessary to add a large amount of AES resin in order to improve the impact resistance of the molded product. The derived surface hardness (scratch resistance) and the heat resistance derived from the maleimide copolymer are significantly reduced.
In addition, since it is necessary to add an AES resin having a relatively large particle size in order to improve the impact resistance of the molded product, the color developability derived from the hard resin is reduced in the obtained molded product.
In the thermoplastic resin composition (4), AES resin and ASA resin are added in order to suppress a decrease in color developability of the molded product, but the impact resistance of the molded product is higher than when only the AES resin is added. Is inferior.

Rubber reinforced resin materials represented by ABS resin are widely used in various fields such as OA equipment, automobiles, general merchandise, etc. as a resin material with excellent balance of impact resistance, mechanical properties and fluidity during molding. It is used.
However, since the ABS resin is an amorphous (non-crystalline) resin, the friction coefficient (dynamic friction coefficient, fluctuation width of the dynamic friction coefficient) of the molded product is larger than that of the crystalline resins such as polyethylene, polypropylene, and polyacetal.
Therefore, there is a problem that a stick-slip phenomenon occurs in the switch portion of the OA device, the fitting portion of the car audio, and the like due to the vibration of the device, the vibration at the start of the vehicle and the traveling, and the like, and a squeak noise is generated.

For example, the following thermoplastic resin composition has been proposed as a rubber-reinforced resin material capable of obtaining a molded product having a small friction coefficient (dynamic friction coefficient, fluctuation width of the dynamic friction coefficient).
(5) A thermoplastic resin composition obtained by adding polyorganosiloxane as a lubricant to a rubber-reinforced styrene resin (Patent Document 8).
(6) A thermoplastic resin composition obtained by adding a silicone resin having a specific viscosity as a lubricant to rubber-reinforced acrylonitrile-styrene resin containing ABS resin and AES resin (Patent Document 9).
(7) A thermoplastic resin composition in which polytetrafluoroethylene, low molecular weight oxidized polyethylene, or ultrahigh molecular weight polyethylene is added as a lubricant to a rubber-reinforced styrene resin, an olefin resin, and a styrene-butadiene-styrene block copolymer ( Patent Document 10).

In the molded product comprising the thermoplastic resin composition of (5) to (7), the lubricant added to the thermoplastic resin composition bleeds out to the surface of the molded product, thereby improving the lubricity of the molded product. Reduce the friction coefficient.
However, the bleed-out lubricant deteriorates the surface appearance of the molded product, and there is a problem that the lubricity decreases with time due to the gradual loss of the lubricated lubricant.

JP-A-11-001600 JP 2000-119477 A JP 2003-277570 A JP 2008-291158 A JP 2005-132970 A JP 2004-352842 A JP 2004-346187 A Japanese Patent No. 2688619 JP 2011-174029 A JP2011-168186A

The first aspect of the present invention is a material for a thermoplastic resin composition that is excellent in impact resistance and scratch resistance, can provide a molded article excellent in glossiness and color developability, and has good fluidity. An object of the present invention is to provide a suitable graft copolymer.

The second aspect of the present invention is a thermoplastic resin composition having good fluidity, excellent impact resistance and scratch resistance of the resulting molded article, and excellent gloss and color development, and impact resistance. The object is to provide a molded article having excellent scratch resistance, gloss and color development.

The third aspect of the present invention is a thermoplastic resin composition having good flowability and excellent scratch resistance, glossiness, color development, and impact resistance of the resulting molded article, and scratch resistance, glossiness, An object is to provide a molded article having excellent color developability and impact resistance.

The fourth aspect of the present invention is a thermoplastic resin composition having good flowability and excellent scratch resistance, color developability and impact resistance of the obtained molded article, and scratch resistance, color developability and impact resistance. It aims at providing the molded product which is excellent in.

The fifth aspect of the present invention is a thermoplastic resin composition having good flowability and excellent scratch resistance, color development, impact resistance and lubricity of the obtained molded article, and scratch resistance, color development, The object is to provide a molded article excellent in impact resistance and lubricity.

The first aspect of the present invention includes the following aspects.
[1] The weight average molecular weight (Mw) is 17 × 10 ⁴ to 35 × 10 ⁴ , and the molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is In the presence of the ethylene / α-olefin copolymer (A) 1 to 3 or the crosslinked ethylene / α-olefin copolymer (C) obtained by crosslinking the ethylene / α-olefin copolymer (A), A graft copolymer (D) obtained by polymerizing a vinyl monomer mixture (m1) containing an aromatic vinyl compound and a vinyl cyanide compound.
[2] Graft content of the crosslinked ethylene / α-olefin copolymer (C) is 35 to 75% by mass based on the total mass of the crosslinked ethylene / α-olefin copolymer (C) Copolymer.
[3] The graft copolymer according to [1] or [2], wherein the ethylene / α-olefin copolymer (A) is an ethylene / propylene copolymer.
[4] The ethylene unit content of the ethylene / α-olefin copolymer (A) is 45 to 65 based on the total mass of the structural units constituting the ethylene / α-olefin copolymer (A). The graft copolymer according to any one of [1] to [3], wherein the graft copolymer is% by mass.
[5] The graft copolymer according to any one of [1] to [4], wherein the polymerization is emulsion polymerization.

The thermoplastic resin composition in the second aspect of the present invention includes the following aspects.
[6] A thermoplastic resin composition comprising the graft copolymer (D) according to any one of [1] to [5] and a hard component (J).
[7] The thermoplastic resin composition according to [6], wherein the hard component (J) is a styrene copolymer (H).

The thermoplastic resin composition according to the third aspect of the present invention includes the following aspects.
[8] Methacrylic acid obtained by polymerizing the graft copolymer (D) according to any one of [1] to [5] and a vinyl monomer mixture (m3) containing a methacrylic ester. A thermoplastic resin composition comprising an ester resin (G).

The thermoplastic resin composition according to the fourth aspect of the present invention includes the following aspects.
[9] An aromatic vinyl compound and cyanide in the presence of the graft copolymer (D) according to any one of [1] to [5]; and a crosslinked acrylate rubber polymer (E). Obtained by polymerizing a graft copolymer (F) obtained by polymerizing a vinyl monomer mixture (m2) containing a vinyl chloride compound; and a vinyl monomer mixture (m3) containing a methacrylate ester An ethylene / α-olefin copolymer (A) or a crosslinked ethylene / α-olefin copolymer contained in the graft copolymer (D) in the thermoplastic resin composition The volume average particle diameter of (C) is 0.2 μm to 0.6 μm; the crosslinked acrylic acid ester rubber-like polymer (E) contained in the graft copolymer (F) in the thermoplastic resin composition Volume average particle diameter is 0.0 μm to 0.18 μm; total of ethylene / α-olefin copolymer (A), crosslinked ethylene / α-olefin copolymer (C) and crosslinked acrylic ester rubbery polymer (E) (100 mass) %) Of the ethylene / α-olefin copolymer (A) or the crosslinked ethylene / α-olefin copolymer (C) is 15 to 85% by mass, and the crosslinked acrylate rubber polymer A thermoplastic resin composition having a ratio of (E) of 85 to 15% by mass.

The thermoplastic resin composition according to the fifth aspect of the present invention includes the following aspects.
[10] In the presence of the graft copolymer (D) according to any one of [1] to [5] and a composite rubber-like polymer (L) containing polyorganosiloxane (La), A graft copolymer (M) obtained by polymerizing the monomer mixture (m5); a methacrylate ester resin (G) obtained by polymerizing a vinyl monomer mixture (m3) containing a methacrylate ester The volume average particle of the ethylene / α-olefin copolymer (A) or the crosslinked ethylene / α-olefin copolymer (C) contained in the graft copolymer (D) in the thermoplastic resin composition The volume average particle size of the composite rubber-like polymer (L) contained in the graft copolymer (M) in the thermoplastic resin composition is 0.05 μm to 0 μm. 18μm; both ethylene and α-olefin Of the total (100% by mass) of the polymer (A), the crosslinked ethylene / α-olefin copolymer (C) and the composite rubbery polymer (L), the ethylene / α-olefin copolymer (A) or the crosslinked ethylene A thermoplastic resin composition in which the proportion of the α-olefin copolymer (C) is 15 to 85% by mass and the proportion of the composite rubbery polymer (L) is 85 to 15% by mass.
[11] The graft copolymer (M) is a unit derived from polyorganosiloxane (La) and (meth) acrylic acid ester, a unit derived from a crosslinking agent, or a unit derived from a graft crossing agent. A vinyl monomer component (m5) containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of a composite rubber-like polymer (L1) comprising a poly (meth) acrylic acid ester (Lb) having one or both The thermoplastic resin composition according to [10], which is obtained by polymerization of

The molded article according to the sixth aspect of the present invention includes the following aspects.
[12] A molded article formed from the thermoplastic resin composition according to any one of [6] to [11].

The graft copolymer according to the first aspect of the present invention has excellent impact resistance and scratch resistance, can give a molded article excellent in glossiness and color developability, and has good fluidity. It is suitable as a material for the resin composition.

The thermoplastic resin composition according to the second aspect of the present invention has good fluidity.
Moreover, according to the thermoplastic resin composition in the second aspect of the present invention, a molded product having excellent impact resistance and scratch resistance, and excellent glossiness and color developability can be obtained.
The molded article using the thermoplastic resin composition according to the second aspect of the present invention is excellent in scratch resistance, gloss, color development, and impact resistance.

The thermoplastic resin composition according to the third aspect of the present invention has good fluidity.
Moreover, according to the thermoplastic resin composition in the third aspect of the present invention, a molded article excellent in scratch resistance, gloss, color development and impact resistance can be obtained.
The molded article using the thermoplastic resin composition according to the third aspect of the present invention is excellent in scratch resistance, gloss, color development and impact resistance.

The thermoplastic resin composition according to the fourth aspect of the present invention has good fluidity. In addition, according to the thermoplastic resin composition of the fourth aspect of the present invention, a molded article having excellent scratch resistance, color developability and impact resistance can be obtained.
The molded article using the thermoplastic resin composition according to the fourth aspect of the present invention is excellent in scratch resistance, color development and impact resistance.

The thermoplastic resin composition according to the fifth aspect of the present invention has good fluidity.
Moreover, according to the thermoplastic resin composition in the fifth aspect of the present invention, a molded article having excellent scratch resistance, color development, impact resistance and lubricity can be obtained.
The molded article using the thermoplastic resin composition according to the fifth aspect of the present invention is excellent in scratch resistance, color development, impact resistance and lubricity.

It is the schematic explaining the abrasion-resistance test by gauze wear. It is the schematic explaining the evaluation method of lubricity.

The following definitions of terms apply throughout this specification and the claims.
“Unit” and “structural unit” mean a monomer unit (monomer unit) constituting a polymer compound (resin, polymer, copolymer).
“(Meth) acrylic acid” means acrylic acid or methacrylic acid.
“Molded product” means a product formed by molding a thermoplastic resin composition.
“Scratch resistance” refers to the resistance to scratches (scratch resistance) caused by scratching the surface of a molded article with a hard, pointed object such as a nail, and work gloves, gauze, cloth, etc. It means both scratch resistance (scratch resistance) against scratches (scratches) that occur when the surface of a molded product is rubbed with a soft material.
“Lightness (L ^* )” means a lightness value (L ^* ) among color values in the L ^* a ^* b ^* color system adopted in JIS Z 8729.
The “SCE method” means a method of measuring a color by using a spectrocolorimeter in accordance with JIS Z 8722 and removing specularly reflected light with an optical trap.

Hereinafter, the present invention will be described in detail.
“Graft Copolymer (D)”
The graft copolymer (D) in the first embodiment of the present invention is an ethylene / α-olefin copolymer (A) or a crosslinked ethylene / α-olefin obtained by crosslinking the ethylene / α-olefin copolymer (A). The vinyl monomer mixture (m1) is polymerized in the presence of the copolymer (C).
In the present invention, “the ethylene / α-olefin copolymer (A) is subjected to a crosslinking treatment” means not only the case where the ethylene / α-olefin copolymer (A) is crosslinked alone, but also the ethylene / α-olefin copolymer (A). -When a mixture of the olefin copolymer (A) and the acid-modified olefin polymer (K) described later is subjected to a crosslinking treatment, or when the ethylene / α-olefin copolymer (A) or the mixture is mixed with an aqueous olefin resin dispersion ( Including the case of crosslinking treatment after B).
In the present specification, “crosslinking treatment” means that polymer chains are linked within a molecule and / or between molecules.
The crosslinked ethylene / α-olefin copolymer (C) was obtained by crosslinking the ethylene / α-olefin copolymer (A) alone and the acid-modified olefin polymer (K) alone. It may be a mixture with things.

Hereafter, each component which comprises the graft copolymer (D) in the 1st aspect of this invention is demonstrated.
In the following, the “thermoplastic resin composition (I)” in the second aspect of the present invention includes the graft copolymer (D) in the first aspect of the present invention, the hard component (J) described later, and It contains.
The “molded product” is formed by molding the thermoplastic resin composition (I).

<Ethylene / α-olefin copolymer (A)>
In the present invention, it is important to use the ethylene / α-olefin copolymer (A) so that the molded article exhibits excellent impact resistance.
The ethylene / α-olefin copolymer (A) is a copolymer comprising ethylene units and α-olefin units, obtained by copolymerizing ethylene and α-olefins by a known polymerization method. Does not contain non-conjugated diene units such as ethylidene-2-norbornene.
For example, when an ethylene / propylene / non-conjugated diene copolymer is used instead of the ethylene / α-olefin copolymer (A), the impact resistance of the molded article is lowered.

As the α-olefin, those having 3 or more carbon atoms are preferable, and specifically, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene. , 1-icosene, 1-docosene and the like. Among these, α-olefins having 3 to 20 carbon atoms are preferable, and propylene is particularly preferable.
When the ethylene / α-olefin copolymer (A) is an ethylene / propylene copolymer in which the α-olefin is propylene, the impact resistance and color developability of the molded product are particularly excellent.

The ethylene unit content of the ethylene / α-olefin copolymer (A) is 45 to 45% when the total of all the structural units constituting the ethylene / α-olefin copolymer (A) is 100% by mass. It is preferably 65% by mass, and more preferably 50 to 60% by mass.
When the ethylene unit content is within the above range, the balance of scratch resistance and impact resistance of the molded product is excellent. Particularly when the ethylene unit content is 50 to 60% by mass, the scratch resistance and impact resistance of the molded product are further improved.
Here, the “ethylene unit content” means the total mass of monomers used in the synthesis of the ethylene / α-olefin copolymer (A) (that is, constituting the ethylene / α-olefin copolymer (A)). The total mass of the monomer corresponding to the structural unit to be calculated) can be calculated from the mass of the monomer corresponding to the ethylene unit.

In the present invention, in order to improve the fluidity of the thermoplastic resin composition (I) and to exhibit excellent scratch resistance, glossiness and impact resistance of the molded article, the mass average molecular weight (Mw), and the mass The use of an ethylene / α-olefin copolymer (A) having a specific molecular weight distribution (Mw / Mn) represented by the ratio of the average molecular weight (Mw) to the number average molecular weight (Mn) is a cross-linked ethylene. -It is important from the viewpoint of controlling the cross-linked structure of the α-olefin copolymer (C).

The mass average molecular weight (Mw) of the ethylene / α-olefin copolymer (A) is 17 × 10 ⁴ to 35 × 10 ⁴ , preferably 26 × 10 ⁴ to 32 × 10 ⁴ .
When the mass average molecular weight (Mw) is smaller than 17 × 10 ⁴ , the scratch resistance and impact resistance of the molded product are inferior. On the other hand, when the mass average molecular weight (Mw) is larger than 35 × 10 ⁴ , the fluidity of the thermoplastic resin composition (I) and the gloss of the molded product are inferior. When the mass average molecular weight (Mw) is in the range of 26 × 10 ⁴ to 32 × 10 ⁴ , the fluidity of the thermoplastic resin composition (I) and the scratch resistance, impact resistance, and gloss of the molded product Is particularly excellent.

The molecular weight distribution (Mw / Mn) represented by the ratio between the mass average molecular weight (Mw) and the number average molecular weight (Mn) of the ethylene / α-olefin copolymer (A) is 1 to 3, and 1.9 to 2.5 is preferred.
When the molecular weight distribution (Mw / Mn) is larger than 3, the molded article has poor scratch resistance and impact resistance. When the molecular weight distribution (Mw / Mn) is 1.9 to 2.5, the fluidity of the thermoplastic resin composition (I), the scratch resistance and the impact resistance of the molded product are particularly excellent.

The mass average molecular weight (Mw) and number average molecular weight (Mn) of the ethylene / α-olefin copolymer (A) are values measured by gel permeation chromatography (GPC) and converted to standard polystyrene.

The ethylene / α-olefin copolymer (A) used in the present invention is not limited in its production method, but is usually produced using a metallocene catalyst or a Ziegler-Natta catalyst. .

Examples of the metallocene catalyst include a combination of an organic compound having a cyclopentadienyl skeleton with a transition metal such as zirconium, titanium, or hafnium, a metallocene complex in which a halogen atom or the like is coordinated, and an organoaluminum compound or an organoboron compound. It is done.
Examples of the Ziegler-Natta catalyst include a catalyst in which a transition metal halide such as titanium, vanadium, zirconium, and hafnium is combined with an organoaluminum compound or an organoboron compound.

Examples of the polymerization method for polymerizing the ethylene / α-olefin copolymer (A) include a method of copolymerizing ethylene and an α-olefin in a solution in the presence of the above catalyst. In this case, a hydrocarbon solvent such as benzene, toluene, xylene, pentane, hexane, heptane, octane is usually used. These hydrocarbon solvents may be used individually by 1 type, and 2 or more types may be mixed and used for them. In addition, a raw material α-olefin may be used as a solvent.
By changing the supply conditions of ethylene and α-olefin, the type and amount of molecular weight regulators such as hydrogen, the type and amount of catalyst, the reaction temperature and pressure, etc., the ethylene / α-olefin copolymer The ethylene unit content, mass average molecular weight (Mw), and molecular weight distribution (Mw / Mn) of (A) can be adjusted.
In the first embodiment of the present invention, the ethylene / α-olefin copolymer (A) is represented by <ethylene / α-olefin copolymer (A)> in “thermoplastic resin composition (I)” described later. Copolymers similar to those mentioned can also be used.

<Acid-modified olefin polymer (K)>
As described above, the crosslinked ethylene / α-olefin copolymer (C) includes those obtained by crosslinking the ethylene / α-olefin copolymer (A), and the ethylene / α-olefin copolymer (A) and A mixture with the acid-modified olefin polymer (K) may be cross-linked, or the ethylene / α-olefin copolymer (A) may be cross-linked alone and the acid-modified olefin polymer (K) alone. It may also be a mixture with a cross-linked product.

The acid-modified olefin polymer (K) is obtained by modifying an olefin polymer such as polyethylene or polypropylene having a mass average molecular weight of 1,000 to 5,000 with a compound having a functional group such as an unsaturated carboxylic acid compound. Can be mentioned.
In this specification, “modification” means that a compound having a functional group in a molecular chain or at a molecular end is bound.
Examples of the unsaturated carboxylic acid compound include acrylic acid, maleic acid, itaconic acid, maleic anhydride, itaconic anhydride and maleic acid monoamide.
When the crosslinked ethylene / α-olefin copolymer (C) is a product obtained by crosslinking a mixture of the ethylene / α-olefin copolymer (A) and the acid-modified olefin polymer (K), A monomer mixture can be polymerized stably. In particular, when a vinyl monomer mixture is polymerized by an emulsion polymerization method, the emulsion stability can be increased.

When the crosslinked ethylene / α-olefin copolymer (C) contains the acid-modified olefin polymer (K), the ratio of the acid-modified olefin polymer (K) in the ethylene / α-olefin copolymer (A) The amount is preferably 1 to 40 parts by mass with respect to 100 parts by mass. When the ratio of the acid-modified olefin polymer (K) is within the above range, the balance between the scratch resistance and impact resistance of the molded product is more excellent.

The timing of mixing the acid-modified olefin polymer (K) is not particularly limited, and the ethylene / α-olefin copolymer (A) and the acid-modified olefin polymer (K) may be mixed and then crosslinked. Then, the ethylene / α-olefin copolymer (A) and the acid-modified olefin polymer (K) may be individually crosslinked and then mixed.
The mixing method of the ethylene / α-olefin copolymer (A) and the acid-modified olefin polymer (K) is not particularly limited as long as it can be uniformly dispersed. A kneading method is preferred.

<Olefin resin aqueous dispersion (B)>
The aqueous olefin resin dispersion (B) is obtained by dispersing the ethylene / α-olefin copolymer (A) in an aqueous medium.
As described above, the crosslinked ethylene / α-olefin copolymer (C) may be obtained by crosslinking the ethylene / α-olefin copolymer (A), or the ethylene / α-olefin copolymer. A mixture of (A) and the acid-modified olefin polymer (K) may be subjected to a crosslinking treatment after making the aqueous olefin resin dispersion (B).

The method for preparing the aqueous dispersion of the olefin resin (B) is not limited. For example, the ethylene / α-olefin copolymer (A) or the like by a known melt-kneading means such as a kneader, a Banbury mixer, a multi-screw extruder, or the like. A method in which a mixture of an ethylene / α-olefin copolymer (A) and an acid-modified olefin polymer (K) is melt-kneaded, dispersed by applying mechanical shearing force, and added to an aqueous medium containing an emulsifier; The α-olefin copolymer (A) or the mixture is dissolved in a hydrocarbon solvent such as pentane, hexane, heptane, benzene, toluene, xylene together with an emulsifier, added to an aqueous medium and emulsified, and then sufficiently stirred. A method of distilling off the hydrocarbon solvent is preferred.

The emulsifier that can be used in the preparation of the aqueous dispersion of the olefin resin (B) may be any conventionally used emulsifier such as a long-chain alkyl carboxylate, a sulfosuccinic acid alkyl ester salt, and an alkylbenzene sulfonate. And the like.
In addition, the amount of emulsifier used can suppress thermal coloring of the thermoplastic resin composition (I), and the particle size of the aqueous olefin resin dispersion (B) can be easily controlled. Therefore, when potassium oleate is used as the emulsifier Is preferably 1 to 8 parts by mass with respect to 100 parts by mass of the ethylene / α-olefin copolymer (A).

The volume average particle diameter of the aqueous olefin resin dispersion (B) is preferably 0.2 to 0.5 μm because the physical property balance of the molded product is excellent.
When the volume average particle diameter is within the above range, the impact resistance of the molded product is further improved.
As a method for controlling the volume average particle diameter of the aqueous olefin resin dispersion (B), the type or amount of the emulsifier, the type or content when the acid-modified olefin polymer (K) is used in combination, shear applied during kneading. The method of adjusting force, temperature conditions, etc. is mentioned.

In the present specification, the volume average particle diameter is a value measured by a laser diffraction / light scattering method.

<Crosslinked ethylene / α-olefin copolymer (C)>
The crosslinked ethylene / α-olefin copolymer (C) can be obtained by crosslinking the ethylene / α-olefin copolymer (A). Specifically, a method in which the ethylene / α-olefin copolymer (A) is crosslinked alone; a mixture of the ethylene / α-olefin copolymer (A) and the acid-modified olefin polymer (K) is crosslinked. A method in which the ethylene / α-olefin copolymer (A) and the acid-modified olefin polymer (K) are each subjected to crosslinking treatment alone and then mixed; ethylene / α-olefin copolymer (A) Alternatively, it may be obtained by a method in which a mixture of an ethylene / α-olefin copolymer (A) and an acid-modified olefin polymer (K) is made into an olefin resin aqueous dispersion (B) and then subjected to a crosslinking treatment.

As a crosslinking treatment method, a known crosslinking treatment method such as a crosslinking treatment method using an organic peroxide or a crosslinking treatment using ionizing radiation can be used. Among these, from the viewpoint of the uniformity of the crosslinked structure of the crosslinked ethylene / α-olefin copolymer (C), a crosslinking treatment using an organic peroxide is preferable, and the organic peroxide of the aqueous olefin resin dispersion (B) is preferable. The crosslinking treatment using is particularly preferred.
In the crosslinking treatment with an organic peroxide, the gel content can be easily adjusted by adjusting the amount of the organic peroxide added, the heating temperature, the heating time, and the like.
The volume average particle size of the aqueous dispersion of the crosslinked ethylene / α-olefin copolymer (C) obtained by crosslinking the aqueous dispersion of the olefin resin (B) with an organic peroxide is the olefin resin aqueous dispersion (B). There is no change with respect to the volume average particle diameter.

Examples of the organic peroxide that can be used for the crosslinking treatment include organic peroxides such as peroxyester compounds, peroxyketal compounds, and dialkyl peroxide compounds.
Specific examples of peroxyester compounds include α, α′-bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecano 1-cyclohexyl-1-methylethylperoxyneodecanoate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-butylperoxy Pivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, 1-cyclohexyl- 1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy-2-hexyl Xanoate, t-butylperoxy 2-hexylhexanoate, t-butylperoxyisobutyrate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy3,5 5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-bis (m-toluoylperoxy) hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxyacetate, t-butylperoxy-m-toluoylbenzoate , T-Butylperoxybenzoe And bis (t-butylperoxy) isophthalate.

Specific examples of the peroxyketal compound include 1,1-bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis. (T-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclododecane, 2,2-bis (T-butylperoxy) butane, n-butyl 4,4-bis (t-butylperoxy) valerate, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane .

Specific examples of dialkyl peroxide compounds include α, α′-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane. , T-butylcumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3, and the like.

These organic peroxides may be used alone or in combination of two or more.
Among the above organic peroxides, dialkyl peroxide compounds such as dicumyl peroxide, t-butyl cumyl peroxide, and di-t-butyl peroxide are particularly preferable from the viewpoint of the uniformity of the crosslinked structure. The standard of the amount of t-butylcumyl peroxide used is 100 parts by mass of the ethylene / α-olefin copolymer (A) or the ethylene / α-olefin copolymer (A) and the acid-modified olefin polymer (K). It is usually in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass in total.

In the crosslinking treatment, a polyfunctional compound may be added in order to adjust the gel content of the crosslinked ethylene / α-olefin copolymer (C).
Examples of the polyfunctional compound include divinylbenzene, allyl methacrylate, ethylene glycol dimethacrylate, 1,3-butylene dimethacrylate, tetraethylene glycol diacrylate, triallyl cyanurate, triallyl isocyanurate, pentaerythritol tetraacrylate and the like. It is done.
These polyfunctional compounds may be used individually by 1 type, and may use 2 or more types together.
Of the above polyfunctional compounds, divinylbenzene is preferred. The amount of divinylbenzene used is 100 parts by mass of ethylene / α-olefin copolymer (A) or 100 parts by mass of ethylene / α-olefin copolymer (A) and acid-modified olefin polymer (K). On the other hand, it is usually in the range of 0 to 10 parts by mass.

The crosslinking treatment time is preferably 1 hour to 12 hours, more preferably 2 hours to 8 hours.
The crosslinking treatment temperature is preferably 60 ° C. to 150 ° C., more preferably 100 ° C. to 140 ° C.

In the present invention, the gel content of the crosslinked ethylene / α-olefin copolymer (C) may be within a specific range in order that the molded product exhibits excellent scratch resistance, impact resistance, and color developability. is important.
The gel content of the crosslinked ethylene / α-olefin copolymer (C) is determined based on the total mass of the crosslinked ethylene / α-olefin copolymer (C) from the viewpoint of the balance between scratch resistance and impact resistance of the molded product. On the other hand, it is 35 to 75% by mass, preferably 40 to 70% by mass, and more preferably 45 to 65% by mass. In particular, if the gel content of the crosslinked ethylene / α-olefin copolymer (C) is 35% by mass or more, the color developability of the molded product is improved.

The gel content of the crosslinked ethylene / α-olefin copolymer (C) can be measured as follows.
First, 0.5 g of the cross-linked ethylene / α-olefin copolymer (C) was collected and used as a coagulated powder sample [D1].
The coagulated powder sample [D1] is immersed in 200 mL of 110 ° C. toluene for 5 hours, then filtered through a 200 mesh wire net, the residue is dried, and the mass of the dried product [D2] is measured. The gel content is calculated from (1). When the crosslinked ethylene / α-olefin copolymer (C) is obtained in the form of an aqueous dispersion or solvent dispersion, the aqueous or solvent dispersion of the crosslinked ethylene / α-olefin copolymer (C) is diluted. 0.5 g of the sample coagulated with sulfuric acid, washed with water and dried is taken as a coagulated powder sample [D1].
Gel content rate (mass%) = dry substance amount [D2] (g) / coagulated powder sample mass [D1] (g) × 100 (1)
In the first embodiment of the present invention, as the crosslinked ethylene / α-olefin copolymer (C), a “crosslinked ethylene / α-olefin copolymer (C)” described later in “thermoplastic resin composition (I)” is used. Copolymers similar to those described in> can also be used.

<Vinyl monomer mixture (m1)>
In the first and second aspects of the present invention, the vinyl monomer mixture (m1) is an aromatic vinyl compound (hereinafter also referred to as “aromatic vinyl monomer”) and vinyl cyanide. It is a mixture containing a compound (hereinafter also referred to as “vinyl cyanide monomer”) as an essential component and another vinyl monomer copolymerizable therewith as an optional component.

Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, vinyltoluene, o-ethylstyrene, and o-, p-dichlorostyrene.
These aromatic vinyl monomers may be used alone or in combination of two or more.
Of the above aromatic vinyl monomers, styrene and α-methylstyrene are preferred.

Examples of the vinyl cyanide monomer include acrylonitrile and methacrylonitrile.
These vinyl cyanide monomers may be used alone or in combination of two or more.
Among the above vinyl cyanide monomers, acrylonitrile is preferable.

Examples of other vinyl monomers include acrylic monomers and maleimide monomers.
Examples of acrylic monomers include alkyl acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, and butyl acrylate, and methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate. Examples include acid alkyl esters. Among these, butyl acrylate or methyl methacrylate is preferably used.
Examples of maleimide monomers include maleimide, N-methylmaleimide, N-butylmaleimide, N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4-hydroxyphenyl) maleimide, N-cyclohexylmaleimide N-substituted maleimide monomers such as Among these, N-phenylmaleimide and N-cyclohexylmaleimide are preferable.

In the first aspect and the second aspect of the present invention, the composition of the vinyl monomer mixture (m1) is the fluidity of the thermoplastic resin composition (I), the impact resistance of the molded product, and the thermal stability. 60% to 82% by mass of the aromatic vinyl monomer and 18% to 40% of the vinyl cyanide monomer based on the total mass of the vinyl monomer mixture (m1). % By mass, other vinyl monomers from 0 to 22% by mass (however, the total of aromatic vinyl monomers, vinyl cyanide monomers and other vinyl monomers is 100% by mass) Preferably there is.
In the first aspect and the second aspect of the present invention, the vinyl monomer mixture (m1) is represented by <vinyl monomer mixture (m1)> in the “thermoplastic resin composition (I)”. Monomer mixtures similar to those mentioned can also be used.

<Graft copolymer (D)>
In the first embodiment and the second embodiment of the present invention, the graft copolymer (D) is present in the presence of an ethylene / α-olefin copolymer (A) or a crosslinked ethylene / α-olefin copolymer (C). It is obtained by polymerizing the vinyl monomer mixture (m1) under the following conditions.
As the polymerization method, known polymerization methods such as emulsion polymerization, solution polymerization, suspension polymerization, bulk polymerization and the like can be adopted, but emulsion polymerization is particularly preferable. When the graft copolymer (D) is produced by emulsion polymerization, the molded article is excellent in scratch resistance and gloss.

In the first and second aspects of the present invention, the graft copolymer (D) is an ethylene / α-olefin copolymer (A) or a crosslinked ethylene / α-olefin copolymer (C) 55. Vinyl monomer mixture (m1) 25 to 45% by mass (provided that ethylene / α-olefin copolymer (A) or crosslinked ethylene / α-olefin copolymer (C)) And the vinyl monomer mixture (m1) are preferably 100% by mass). If the ethylene / α-olefin copolymer (A) or the crosslinked ethylene / α-olefin copolymer (C) is 55 to 75% by mass, the flowability of the thermoplastic resin composition (I), The balance of physical properties of slidability, impact resistance and gloss is further improved.

In the first aspect and the second aspect of the present invention, the graft ratio of the graft copolymer (D) is determined by the flowability of the thermoplastic resin composition (I), the impact resistance of the molded article, the color developability, From the viewpoint of further improving the balance of gloss, 25 to 60% by mass is preferable.

In this specification, the graft ratio of the graft copolymer (D) can be measured as follows.
1 g of the graft copolymer (D) is added to 80 mL of acetone and heated to reflux at 65 to 70 ° C. for 3 hours. The resulting suspension acetone solution is centrifuged at 14,000 rpm for 30 minutes in a centrifuge. Then, a precipitation component (acetone insoluble component) and an acetone solution (acetone soluble component) are collected. And the precipitation component (acetone insoluble component) is dried, the mass (Y (g)) is measured, and a graft ratio is computed by following formula (2). In Formula (2), Y is the mass (g) of the acetone-insoluble component of the graft copolymer (D), X is the total mass (g) of the graft copolymer (D) used to determine Y, The rubber fraction is the content ratio of the graft copolymer (D) in terms of solid content of the ethylene / α-olefin copolymer (A) or the crosslinked ethylene / α-olefin copolymer (C).
Graft ratio (mass%) = {(Y−X × rubber fraction) / X × rubber fraction} × 100 (2)

As a method for producing the graft copolymer (D) by emulsion polymerization, for example, an organic peroxide is mixed into the vinyl monomer mixture (m1), and then the vinyl monomer mixture (m1) is ethylene. A method of continuously adding an aqueous dispersion of an α-olefin copolymer (A) (that is, an aqueous dispersion of an olefin resin (B)) or an aqueous dispersion of a crosslinked ethylene / α-olefin copolymer (C) Is mentioned.
In the aqueous dispersion of the ethylene / α-olefin copolymer (A) or the aqueous dispersion of the crosslinked ethylene / α-olefin copolymer (C), the ethylene / α-olefin copolymer (A) or the crosslinked ethylene / α The concentration of the olefin copolymer (C) is preferably 15 to 65% by mass, more preferably 25 to 55% by mass.
The reaction time is preferably 2 hours to 5 hours, more preferably 2.5 hours to 4.5 hours.
The reaction temperature is preferably 50 ° C. to 120 ° C., more preferably 60 ° C. to 95 ° C.
The organic peroxide is preferably used as a redox initiator that combines an organic peroxide, a transition metal, and a reducing agent.
Moreover, you may use a chain transfer agent, an emulsifier, etc. according to a condition in superposition | polymerization.
In addition, you may add antioxidant to a graft copolymer (D) as needed.

As the redox initiator, a combination of an organic peroxide and a ferrous sulfate-chelating agent-reducing agent is preferable.
Examples of the organic peroxide include cumene hydroperoxide, diisopropylbenzene hydroperoxide, t-butyl hydroperoxide, and the like.
More preferred redox initiators are those comprising cumene hydroperoxide, ferrous sulfate, sodium pyrophosphate, and dextrose.

As chain transfer agents, mercaptans (octyl mercaptan, n-, t-dodecyl mercaptan, n-hexadecyl mercaptan, n-, t-tetradecyl mercaptan, etc.), allyl sulfonic acid, methallyl sulfonic acid and sodas thereof Examples include allyl compounds such as salts, and α-methylstyrene dimer. Among these, mercaptans are preferable. Moreover, these chain transfer agents may be used individually by 1 type, and may use 2 or more types together.
The method for adding the chain transfer agent may be any of batch, split, and continuous.
Moreover, the addition amount of the chain transfer agent is preferably 2.0 parts by mass or less with respect to 100 parts by mass of the vinyl monomer mixture (m1).

Examples of the emulsifier include anionic surfactants, nonionic surfactants, and amphoteric surfactants.
Examples of the anionic surfactants include higher alcohol sulfates, alkylbenzene sulfonates, fatty acid sulfonates, phosphate salts, fatty acid salts, and amino acid derivative salts.
Examples of nonionic surfactants include ordinary polyethylene glycol alkyl ester types, alkyl ether types, and alkyl phenyl ether types.
Examples of the amphoteric surfactant include those having a carboxylate salt, sulfate ester salt, sulfonate salt, phosphate ester salt and the like in the anion portion and amine salts and quaternary ammonium salts in the cation portion.
The addition amount of the emulsifier is preferably 10 parts by mass or less with respect to 100 parts by mass of the vinyl monomer mixture (m1).

The graft copolymer (D) thus obtained is in a state dispersed in water. As a method for recovering the graft copolymer (F) from the aqueous dispersion containing the graft copolymer (D), for example, a precipitant is added to the aqueous dispersion, and after heating and stirring, the precipitant is separated. And a precipitation method of washing, dehydrating, and drying.
Examples of the precipitating agent in the precipitation method include aqueous solutions of sulfuric acid, acetic acid, calcium chloride, magnesium sulfate and the like, and these may be used alone or in combination of two or more.
In the first aspect of the present invention, the graft copolymer (D) may be a copolymer similar to that described in the <graft copolymer (D)> in the “thermoplastic resin composition (I)”. Can be used.

The graft copolymer (D) in the first embodiment of the present invention described above is a specific vinyl monomer in the presence of a crosslinked ethylene / α-olefin copolymer (C) having a specific crosslinked structure. Since the mixture (m1) is polymerized, it is possible to obtain a molded article having excellent scratch resistance, impact resistance, glossiness, and color developability, and a thermoplastic resin composition (I ) Is suitable as a material.

"Thermoplastic resin composition (I)"
The thermoplastic resin composition (I) in the second aspect of the present invention contains the graft copolymer (D) and the hard component (J) in the first aspect of the present invention described above.
Although it does not restrict | limit especially as a hard component (J), A styrene-type copolymer (H), a polycarbonate, methacrylic ester resin (G) (for example, polymethyl methacrylate), polybutylene terephthalate, polyethylene terephthalate, polyvinyl chloride, Examples include methyl methacrylate / styrene copolymer, methyl methacrylate / styrene / N-phenylmaleimide copolymer, modified polyphenylene ether, and polyamide. Among these, styrene copolymers and polycarbonate are preferable.
These hard components (J) may be used individually by 1 type, and may use 2 or more types together.
The thermoplastic resin composition (I) of the second aspect contains the respective components contained in the thermoplastic resin composition (I) of the third aspect, the fourth aspect, and the fourth aspect. Also good.

The styrene copolymer (H) contains an aromatic vinyl monomer as an essential component, and a mixture containing a vinyl cyanide monomer and other vinyl monomers copolymerizable therewith as optional components. It is a copolymer consisting of.
Specific examples of the aromatic vinyl monomer, vinyl cyanide monomer and other vinyl monomers include the aromatic vinyl monomers exemplified above in the description of the vinyl monomer mixture (m1). Examples thereof include a monomer, a vinyl cyanide monomer, and other vinyl monomers.
Alternatively, a monomer mixture containing at least an aromatic vinyl compound and a vinyl cyanide compound exemplified in the vinyl monomer mixture (m4) described later can be used.

The composition of the styrenic copolymer (H) is not particularly limited, but is 25 to 100% by mass of an aromatic vinyl monomer, 0 to 40% by mass of a vinyl cyanide monomer, and these monomers. Copolymers obtained by polymerizing 0 to 65% by weight of other vinyl monomers copolymerizable with the polymer (however, aromatic vinyl monomers, vinyl cyanide monomers, other vinyl monomers The total of the masses is 100% by mass).

For the production of the styrene copolymer (H), a polymerization method such as emulsion polymerization or suspension polymerization is employed.
When the styrene copolymer (H) is produced by emulsion polymerization, each monomer, emulsifier, polymerization initiator and chain transfer agent are charged in the reactor in the presence of water, heated to polymerize, and after polymerization. The styrene copolymer (H) is recovered from the aqueous dispersion containing the styrene copolymer (H) by a precipitation method.
Here, general emulsifiers for emulsion polymerization such as potassium rosinate and sodium alkylbenzenesulfonate can be used as the emulsifier. Further, organic and inorganic peroxide initiators can be used as the polymerization initiator, and mercaptans, α-methylstyrene dimers, terpenes, and the like can be used as the chain transfer agent.
As the precipitation method, a method similar to that used when recovering the graft copolymer (D) from the aqueous dispersion obtained after the graft polymerization can be employed.

When the styrene copolymer (H) is produced by suspension polymerization, each monomer, suspending agent, suspending aid, polymerization initiator and chain transfer agent are charged into the reactor and heated to polymerize. The obtained slurry is dehydrated and dried to recover the styrene copolymer.
Here, as the suspending agent, tricalcium phosphite, polyvinyl alcohol or the like can be used, and as the suspending aid, sodium alkylbenzene sulfonate or the like can be used. In addition, organic peroxides can be used as the polymerization initiator, and mercaptans, α-methylstyrene dimer, terpenes, and the like can be used as the chain transfer agent.

Examples of the polycarbonate include those obtained by reacting one or more bisphenols with phosgene or a carbonic acid diester.
Examples of bisphenols include hydroquinone, 4,4-dihydroxyphenyl, bis- (4-hydroxyphenyl) -alkane, bis- (4-hydroxyphenyl) -cycloalkane, bis- (4-hydroxyphenyl) -sulfide, Examples include bis- (4-hydroxyphenyl) -ether, bis- (4-hydroxyphenyl) -ketone, bis- (4-hydroxyphenyl) -sulfone, or alkyl-substituted, aryl-substituted, and halogen-substituted products thereof. It is done. Among these, 2,2-bis- (4-hydroxyphenyl) propane, a so-called bisphenol A-based polycarbonate using bisphenol A as a raw material is preferable because it can be easily obtained. These may be used alone or in combination of two or more.

The thermoplastic resin composition (I) in the third aspect of the present invention contains a graft copolymer (D) and a methacrylic ester resin (G).
The thermoplastic resin composition (I) in the fourth aspect of the present invention includes a graft copolymer (D), a graft copolymer (F), and a methacrylic ester resin (G).
The thermoplastic resin composition in the fifth aspect of the present invention comprises (I), a graft copolymer (D), a graft copolymer (M), and a methacrylic ester resin (G).
The thermoplastic resin composition (I) in the third aspect, the fourth aspect, and the fifth aspect of the present invention is a styrenic copolymer within the range that does not impair the effects of the present invention. (H), other thermoplastic resins, and various additives may be included.

The graft copolymer (D) in the third aspect, the fourth aspect, and the fifth aspect is the following (α) or (β).
(Α) A product obtained by polymerizing the vinyl monomer mixture (m1) in the presence of the ethylene / α-olefin copolymer (A).
(Β) A product obtained by polymerizing the vinyl monomer mixture (m1) in the presence of the crosslinked ethylene / α-olefin copolymer (C).

Specific examples of (α) include the following.
(Α1) A product obtained by polymerizing the vinyl monomer mixture (m1) in a solution containing the ethylene / α-olefin copolymer (A).
(Α2) A product obtained by polymerizing a vinyl monomer mixture (m1) in an aqueous olefin resin dispersion (B) containing an ethylene / α-olefin copolymer (A).

Specific examples of (β) include the following.
(Β1) A product obtained by polymerizing the vinyl monomer mixture (m1) in a solution containing the crosslinked ethylene / α-olefin copolymer (C).
(Β2) A product obtained by polymerizing the vinyl monomer mixture (m1) in an aqueous dispersion containing the crosslinked ethylene / α-olefin copolymer (C).

The graft copolymer (F) is the following (γ).
(Γ) A product obtained by polymerizing the vinyl monomer mixture (m2) in the presence of the crosslinked acrylic ester rubber-like polymer (E).

The methacrylic ester resin (G) is the following (δ).
(Δ) A product obtained by polymerizing the vinyl monomer mixture (m3).

The styrene copolymer (H) is the following (ε).
(Ε) A product obtained by polymerizing a vinyl monomer mixture (m4).

The graft copolymer (M) is the following (ζ).
(Ζ) Rubber-like polymer (L) containing polyorganosiloxane (La) (preferably, composite rubber-like polymer (L1) comprising polyorganosiloxane (La) and poly (meth) acrylic acid ester (Lb)) Obtained by polymerizing a vinyl monomer mixture (m5) in the presence of.
Each component ((A) to (H), (K), (L), (L1), (La), (Lb), (M), (m1) to (m5), etc.) will be described below.

<Ethylene / α-olefin copolymer (A)>
In the present invention, it is important to use the ethylene / α-olefin copolymer (A) so that the molded article exhibits excellent impact resistance.
The ethylene / α-olefin copolymer (A) comprises an ethylene unit and an α-olefin unit obtained by copolymerizing ethylene and an α-olefin having 3 or more carbon atoms by a known polymerization method. It is a copolymer.

Examples of the α-olefin include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-icosene, 1-docosene, etc. From the viewpoint of impact resistance, α-olefins having 3 to 20 carbon atoms are preferred, and propylene is particularly preferred.

The ethylene unit content of the ethylene / α-olefin copolymer (A) is 45 to 45% when the total of all the structural units constituting the ethylene / α-olefin copolymer (A) is 100% by mass. 65% by mass is preferable, and 50 to 60% by mass is more preferable. When the ethylene unit content is within the above range, the balance of scratch resistance and impact resistance of the molded product is further improved. In particular, when the ethylene unit content is 50 to 60% by mass, the scratch resistance and impact resistance of the molded product are further improved.
Here, the “ethylene unit content” means the total mass of monomers used in the synthesis of the ethylene / α-olefin copolymer (A) (that is, constituting the ethylene / α-olefin copolymer (A)). The total mass of the monomer corresponding to the structural unit to be calculated) can be calculated from the mass of the monomer corresponding to the ethylene unit.

In the present invention, the flowability of the thermoplastic resin composition (I) is improved, and the molded article exhibits excellent scratch resistance, gloss, color development, impact resistance and lubricity, so that the mass average molecular weight is improved. (Mw), and an ethylene / α-olefin copolymer (A) having a molecular weight distribution (Mw / Mn) represented by a ratio of mass average molecular weight (Mw) to number average molecular weight (Mn) in a specific range. It is important to use.

The mass average molecular weight (Mw) of the ethylene / α-olefin copolymer (A) is 17 × 10 ⁴ to 35 × 10 ⁴ , preferably 26 × 10 ⁴ to 32 × 10 ⁴ . When the mass average molecular weight (Mw) is smaller than 17 × 10 ⁴ , the scratch resistance, impact resistance, and lubricity of the molded product are inferior. On the other hand, when the mass average molecular weight (Mw) is larger than 35 × 10 ⁴ , the fluidity of the thermoplastic resin composition (I) and the glossiness, color development, and lubricity of the molded product are inferior. When the mass average molecular weight (Mw) is 26 × 10 ⁴ to 32 × 10 ⁴ , the fluidity of the thermoplastic resin composition (I) and the scratch resistance, impact resistance, gloss, and lubricity of the molded product Is even better.

The molecular weight distribution (Mw / Mn) of the ethylene / α-olefin copolymer (A) is 1 to 3, and preferably 1.9 to 2.5. When the molecular weight distribution (Mw / Mn) is larger than 3, the molded article is inferior in scratch resistance, impact resistance, and lubricity. When the molecular weight distribution (Mw / Mn) is 1.9 to 2.5, the fluidity of the thermoplastic resin composition (I), the scratch resistance and the impact resistance of the molded product are further improved.

The method for producing the ethylene / α-olefin copolymer (A) is not limited. The ethylene / α-olefin copolymer (A) is usually produced by polymerizing ethylene and an α-olefin using a metallocene catalyst or a Ziegler-Natta catalyst.

As a metallocene catalyst, a catalyst obtained by combining an organic compound having a cyclopentadienyl skeleton with a transition metal (zirconium, titanium, hafnium, etc.), a metallocene complex coordinated with a halogen atom, etc., and an organoaluminum compound, organoboron compound, etc. Is mentioned.
Examples of the Ziegler-Natta catalyst include a catalyst obtained by combining a halide of a transition metal (titanium, vanadium, zirconium, hafnium, etc.) with an organoaluminum compound, an organoboron compound, or the like.

Examples of the polymerization method include a method of copolymerizing ethylene and α-olefin in a solvent in the presence of the catalyst. Examples of the solvent include hydrocarbon solvents (benzene, toluene, xylene, pentane, hexane, heptane, octane, etc.). A hydrocarbon solvent may be used individually by 1 type, and 2 or more types may be mixed and used for it. In addition, a raw material α-olefin may be used as a solvent.

Ethylene / α-olefin copolymer (A) by changing reaction conditions such as supply amount of ethylene, α-olefin, type and amount of molecular weight regulator such as hydrogen, type and amount of catalyst, reaction temperature, pressure, etc. ) Ethylene unit content, mass average molecular weight (Mw) and molecular weight distribution (Mw / Mn) can be adjusted.

<Olefin resin aqueous dispersion (B)>
The aqueous olefin resin dispersion (B) is obtained by dispersing the ethylene / α-olefin copolymer (A) in an aqueous medium.

The method for preparing the aqueous olefin resin dispersion (B) is not limited. As a preparation method, for example, the ethylene / α-olefin copolymer (A) is melt-kneaded by a known melt-kneading means (kneader, Banbury mixer, multi-screw extruder, etc.) and dispersed by applying mechanical shearing force. The ethylene / α-olefin copolymer (A) is dissolved in a hydrocarbon solvent (pentane, hexane, heptane, benzene, toluene, xylene, etc.) together with the emulsifier, and added to the aqueous medium. After adding and emulsifying, there may be mentioned a method of sufficiently stirring and distilling off the hydrocarbon solvent. In preparing the aqueous olefin resin dispersion (B), an emulsifier, an acid-modified olefin polymer (K), and the like may be added as other components.

Examples of the emulsifier include known ones, and examples thereof include long-chain alkyl carboxylates, sulfosuccinic acid alkyl ester salts, and alkylbenzene sulfonates.
In the case of using potassium oleate as an emulsifier, the added amount of the emulsifier can suppress thermal coloring of the resulting thermoplastic resin composition (I) and can easily control the particle size of the aqueous olefin resin dispersion (B). The amount of the ethylene / α-olefin copolymer (A) is preferably 1 to 8 parts by mass with respect to 100 parts by mass.

As the acid-modified olefin polymer (K), an olefin polymer having a mass average molecular weight of 1,000 to 5,000 (polyethylene, polypropylene, etc.) was modified with a compound having a functional group (such as an unsaturated carboxylic acid compound). Things. Examples of the unsaturated carboxylic acid compound include acrylic acid, maleic acid, itaconic acid, maleic anhydride, itaconic anhydride, maleic acid monoamide, and the like.
The addition amount of the acid-modified olefin polymer (K) is preferably 1 to 40 parts by mass with respect to 100 parts by mass of the ethylene / α-olefin copolymer (A). When the addition amount of the acid-modified olefin polymer (K) is within the above range, the balance between the scratch resistance and impact resistance of the molded product is further improved.

The method for adding the acid-modified olefin polymer (K) is not limited. The ethylene / α-olefin copolymer (A) and the acid-modified olefin polymer (K) may be mixed and then subjected to crosslinking treatment, or the ethylene / α-olefin copolymer (A) and the acid-modified olefin polymer may be polymerized. The union (K) may be mixed after the crosslinking treatment.
The mixing method of the ethylene / α-olefin copolymer (A) and the acid-modified olefin polymer (K) is not limited. Examples of the mixing method include a melt kneading method using a kneader, a Banbury mixer, a multi-screw extruder and the like.

The volume average particle diameter of the ethylene / α-olefin copolymer (A) in the aqueous olefin resin dispersion (B) is preferably 0.2 to 0.6 μm from the viewpoint of excellent physical property balance of the molded product. More preferably, it is 3 to 0.5 μm. When the volume average particle diameter is within the above range, the impact resistance, color developability and lubricity of the molded product are further improved.
The method for controlling the volume average particle diameter of the ethylene / α-olefin copolymer (A) in the aqueous olefin resin dispersion (B) includes the type or amount of emulsifier, the type of acid-modified olefin polymer (K). Or the method of adjusting content, the shear force added at the time of kneading | mixing, temperature conditions, etc. is mentioned.
The volume average particle diameter of the ethylene / α-olefin copolymer (A) or the crosslinked ethylene / α-olefin copolymer (C) dispersed in the aqueous dispersion is the same as that of the thermoplastic resin composition (I). It has been confirmed by image processing of an electron micrograph that the volume average particle diameter of the α-olefin copolymer (A) and the crosslinked ethylene / α-olefin copolymer (C) is shown.

<Crosslinked ethylene / α-olefin copolymer (C)>
In the third, fourth and fifth aspects of the present invention, the crosslinked ethylene / α-olefin copolymer (C) is obtained by crosslinking the ethylene / α-olefin copolymer (A). It is preferable that

In the third aspect, the fourth aspect, and the fifth aspect of the present invention, in order for the molded product to exhibit excellent scratch resistance, impact resistance, and color developability, the crosslinked ethylene / α-olefin copolymer is used. The gel content of the coalesced (C) is preferably in a specific range.
In the third aspect, the fourth aspect, and the fifth aspect of the present invention, the gel content of the crosslinked ethylene / α-olefin copolymer (C) is determined depending on the scratch resistance, impact resistance, and coloring of the molded product. From the viewpoint of balance with the properties, it is preferably 35 to 75% by mass, more preferably 40 to 70% by mass, and particularly preferably 45 to 65% by mass with respect to the total mass of the crosslinked ethylene / α-olefin copolymer (C). preferable.

The crosslinking treatment of the ethylene / α-olefin copolymer (A) is performed by a known method. As a crosslinking treatment method, (a) a method of carrying out a crosslinking treatment by adding an organic peroxide and, if necessary, a polyfunctional compound to the ethylene / α-olefin copolymer (A); ) A method of performing a crosslinking treatment with ionizing radiation, and the like, and the method (a) is preferable from the viewpoint of impact resistance and color developability of the molded product.

Specifically, the method (a) includes an ethylene / α-olefin copolymer (A) or an aqueous olefin resin dispersion (B), an organic peroxide, and, if necessary, a polyfunctional compound. The method of adding and heating is mentioned.
The gel content of the crosslinked ethylene / α-olefin copolymer (C) can be adjusted by adjusting the addition amount of organic peroxide and polyfunctional compound, heating temperature, heating time, and the like.
The heating temperature varies depending on the type of organic peroxide. The heating temperature is preferably −5 ° C. to + 30 ° C., which is the 10-hour half-life temperature of the organic peroxide.
The heating time is preferably 3 to 15 hours.

The organic peroxide is for forming a crosslinked structure in the ethylene / α-olefin copolymer (A). Examples of the organic peroxide include a peroxy ester compound, a peroxy ketal compound, a dialkyl peroxide compound, and the like. An organic peroxide may be used individually by 1 type, and may be used in combination of 2 or more type.

Specific examples of the peroxyester compound include α, α′-bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1 -Cyclohexyl-1-methylethylperoxyneodecanoate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-butylperoxypivalate, 1,1, 3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, 1-cyclohexyl-1-methylethylperoxy-2-ethyl Hexanoate, t-hexylperoxy 2-hexyl Ruhexanoate, t-butylperoxy 2-hexylhexanoate, t-butylperoxyisobutyrate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy 3,5,5-trimethylhexano Ate, t-butylperoxylaurate, 2,5-dimethyl-2,5-bis (m-toluoylperoxy) hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate, t-hexyl Peroxybenzoate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxyacetate, t-butylperoxy-m-toluoylbenzoate, t-butylperoxybenzo Chromatography, bis (t-butylperoxy) isophthalate.

Specific examples of the peroxyketal compound include 1,1-bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t- Butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclododecane, 2,2-bis (t-butylperoxy) Examples include butane, n-butyl 4,4-bis (t-butylperoxy) valerate, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, and the like.

Specific examples of the dialkyl peroxide compound include α, α′-bis (t-butyl peroxide) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, and t-butyl. Examples include cumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3.

Organic peroxides include dialkyls such as dicumyl peroxide, t-butylcumyl peroxide, and di-t-butyl peroxide because the gel content of the crosslinked ethylene / α-olefin copolymer (C) can be easily adjusted. Peroxide compounds are particularly preferred.

The amount of the organic peroxide added is that the gel content of the cross-linked ethylene / α-olefin copolymer (C) can be easily adjusted to a range of 35 to 75% by mass, so that the ethylene / α-olefin copolymer (A ) 0.1 to 5 parts by mass is preferable with respect to 100 parts by mass.

The polyfunctional compound is used in combination with an organic peroxide as necessary in order to adjust the gel content of the crosslinked ethylene / α-olefin copolymer (C). Examples of the polyfunctional compound include divinylbenzene, allyl methacrylate, ethylene glycol dimethacrylate, 1,3-butylene dimethacrylate, tetraethylene glycol diacrylate, triallyl cyanurate, triallyl isocyanurate, pentaerythritol tetraacrylate, and the like. From the viewpoint of easily adjusting the gel content, divinylbenzene is preferred. A polyfunctional compound may be used individually by 1 type, and may be used in combination of 2 or more type.

The addition amount of the polyfunctional compound is such that the gel content of the crosslinked ethylene / α-olefin copolymer (C) can be easily adjusted to 35 to 75% by mass, so that the ethylene / α-olefin copolymer (A) 100 is added. 10 parts by mass or less is preferable with respect to parts by mass.

The volume average particle diameter of the crosslinked ethylene / α-olefin copolymer (C) in the aqueous dispersion is 0.2 to 0.6 μm, and 0.3 to 0.5 μm in view of excellent physical properties of the molded product. Is preferred.
When the volume average particle diameter is in the above range, the molded article is excellent in impact resistance, color developability and lubricity.

Volume average of crosslinked ethylene / α-olefin copolymer (C) in aqueous dispersion of crosslinked ethylene / α-olefin copolymer (C) obtained by crosslinking olefin resin aqueous dispersion (B) with organic peroxide The particle diameter does not change with respect to the volume average particle diameter of the ethylene / α-olefin copolymer (A) in the aqueous olefin resin dispersion (B).

<Vinyl monomer mixture (m1)>
In the third aspect, the fourth aspect, and the fifth aspect of the present invention, the vinyl monomer mixture (m1) is a monomer mixture containing at least an aromatic vinyl compound and a vinyl cyanide compound.

Examples of the aromatic vinyl compound include styrene, α-methyl styrene, o-, m- or p-methyl styrene, vinyl xylene, pt-butyl styrene, ethyl styrene, and the like. Styrene and α-methylstyrene are preferred from the viewpoint of the fluidity of I), the color developability of the molded product, and the impact resistance. An aromatic vinyl compound may be used individually by 1 type, and may be used in combination of 2 or more type.
The content of the aromatic vinyl compound is preferably 65 to 82% by mass, more preferably 73 to 80% by mass, and further preferably 75 to 80% by mass in 100% by mass of the vinyl monomer mixture (m1). When the content of the aromatic vinyl compound is within the above range, the color developability and impact resistance of the molded product are further improved.

Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. A vinyl cyanide compound may be used individually by 1 type, and may be used in combination of 2 or more type.
In the third aspect, the fourth aspect, and the fifth aspect of the present invention, the content of the vinyl cyanide compound is preferably 18 to 35% by mass in 100% by mass of the vinyl monomer mixture (m1), It is more preferably 20 to 27% by mass, and further preferably 20 to 25% by mass. When the content of the vinyl cyanide compound is within the above range, the color developability and impact resistance of the molded product are further improved.

The vinyl monomer mixture (m1) may contain, in addition to the aromatic vinyl compound and the vinyl cyanide compound, other monomers copolymerizable therewith within a range not impairing the effects of the present invention.
Other monomers include acrylic acid esters (methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, etc.), methacrylic acid esters (methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, etc.) ), Maleimide compounds (N-cyclohexylmaleimide, N-phenylmaleimide, etc.) and the like.
Another monomer may be used individually by 1 type and may be used in combination of 2 or more type.

<Graft copolymer (D)>
In the third aspect, the fourth aspect, and the fifth aspect of the present invention, the graft copolymer (D) is an ethylene / α-olefin copolymer (A) or a crosslinked ethylene / α-olefin copolymer. It can be obtained by polymerizing the vinyl monomer mixture (m1) in the presence of (C).

Since the graft copolymer (D) can sufficiently secure a molecular chain (graft component) contributing to elastic deformation, the ethylene / α-olefin copolymer contained in the graft copolymer (D) under shear stress (A) Deformation of the particles or crosslinked ethylene / α-olefin copolymer (C) particles is suppressed. Therefore, by blending the graft copolymer (D), the molded product can exhibit excellent impact resistance and scratch resistance.

In the third aspect, the fourth aspect, and the fifth aspect of the present invention, the graft copolymer (D) is an ethylene / α-olefin copolymer (A) or a crosslinked ethylene / α-olefin copolymer. (C) In the presence of 50 to 80% by mass, vinyl monomer mixture (m1) 20 to 50% by mass (provided that ethylene / α-olefin copolymer (A) or crosslinked ethylene / α-olefin copolymer) What was obtained by superposing | polymerizing a coalescence (C) and a vinyl-type monomer mixture (m1) is 100 mass%) is preferable. If the ethylene / α-olefin copolymer (A) or the crosslinked ethylene / α-olefin copolymer (C) is 50 to 80% by mass, the fluidity of the thermoplastic resin composition (I), The balance of physical properties of impact resistance, gloss and color development is further improved. Further, in the presence of 55 to 75% by mass of the ethylene / α-olefin copolymer (A) or crosslinked ethylene / α-olefin copolymer (C), the vinyl monomer mixture (m1) is 25 to 45% by mass. (However, the total of the ethylene / α-olefin copolymer (A) or the crosslinked ethylene / α-olefin copolymer (C) and the vinyl monomer mixture (m1) is 100% by mass). More preferred.

In the third aspect, the fourth aspect, and the fifth aspect of the present invention, the graft ratio of the graft copolymer (D) is determined by the flowability of the thermoplastic resin composition (I) and the impact resistance of the molded product. From the viewpoint of the balance between color development and gloss, it is preferably 20 to 100% by mass.

Examples of the polymerization method include known polymerization methods (emulsion polymerization method, solution polymerization method, suspension polymerization method, bulk polymerization method, etc.), and emulsion polymerization method from the point that the scratch resistance and gloss of the molded product are further improved. Is particularly preferred.

As a method for producing the graft copolymer (D) by the emulsion polymerization method, for example, an organic peroxide is mixed into the vinyl monomer mixture (m1), and then the vinyl monomer mixture (m1) is converted into an olefin. Examples thereof include a method of continuously adding the aqueous resin dispersion (B) or the aqueous dispersion of the crosslinked ethylene / α-olefin copolymer (C).
In the aqueous dispersion of olefin resin aqueous dispersion (B) or crosslinked ethylene / α-olefin copolymer (C), ethylene / α-olefin copolymer (A) or crosslinked ethylene / α-olefin copolymer (C ) Is preferably 15 to 65% by mass, more preferably 25 to 55% by mass.
The reaction time is preferably 2 hours to 5 hours, more preferably 2.5 hours to 4.5 hours.
The reaction temperature is preferably 50 ° C to 100 ° C, more preferably 60 ° C to 90 ° C.
The organic peroxide is preferably used as a redox initiator that combines an organic peroxide, a transition metal, and a reducing agent. In the polymerization, a chain transfer agent, an emulsifier or the like may be used depending on the situation.

Redox initiator does not require high polymerization reaction conditions, avoids deterioration of ethylene / α-olefin copolymer (A) or crosslinked ethylene / α-olefin copolymer (C), etc. A combination of an organic peroxide and a ferrous sulfate-chelating agent-reducing agent is preferable from the viewpoint of avoiding a decrease in impact resistance of the product.
Examples of the organic peroxide include cumene hydroperoxide, diisopropylbenzene hydroperoxide, t-butyl hydroperoxide and the like.
The redox initiator is more preferably composed of cumene hydroperoxide, ferrous sulfate, sodium pyrophosphate, and dextrose.

Chain transfer agents include mercaptans (octyl mercaptan, n- or t-dodecyl mercaptan, n-hexadecyl mercaptan, n- or t-tetradecyl mercaptan, etc.), allyl compounds (allyl sulfonic acid, methallyl sulfonic acid, these Sodium salts, etc.), α-methylstyrene dimers, etc., and mercaptans are preferred from the viewpoint of easy adjustment of the molecular weight. A chain transfer agent may be used individually by 1 type, and may be used in combination of 2 or more type.
The method for adding the chain transfer agent may be any of batch, split, and continuous.
The addition amount of the chain transfer agent is preferably 2.0 parts by mass or less with respect to 100 parts by mass of the vinyl monomer mixture (m1).

The graft copolymer (D) obtained by the emulsion polymerization method is in a state of being dispersed in water.
As a method for recovering the graft copolymer (D) from the aqueous dispersion containing the graft copolymer (D), for example, a precipitation agent is added to the aqueous dispersion, heated and stirred, and then the precipitation agent is separated. And a precipitation method in which the precipitated graft copolymer (D) is washed with water, dehydrated and dried.
Examples of the precipitating agent include aqueous solutions of sulfuric acid, acetic acid, calcium chloride, magnesium sulfate, and the like. A precipitation agent may be used individually by 1 type, and may be used in combination of 2 or more type.
An antioxidant may be added to the aqueous dispersion containing the graft copolymer (D) as necessary.

<Crosslinked acrylic ester-based rubbery polymer (E)>
The cross-linked acrylic ester rubbery polymer (E) is a copolymer having a unit derived from a (meth) acrylic ester, a unit derived from a cross-linking agent, a unit derived from a graft crossing agent, or both. It is a coalescence.
The aqueous dispersion of the crosslinked acrylic ester rubber-like polymer (E) may contain an aqueous dispersion of other rubber components such as polybutadiene.

Examples of (meth) acrylic acid esters include (meth) acrylic acid alkyl esters having an alkyl group having 1 to 12 carbon atoms, and acrylic acid esters having an aromatic hydrocarbon group (phenyl group, benzyl group, etc.). From the viewpoint of impact resistance of the molded product, n-butyl acrylate, 2-ethylhexyl acrylate, and ethyl acrylate are preferred.
One (meth) acrylic acid ester may be used alone, or two or more may be used in combination.

Crosslinking agents and graft crossing agents improve the color developability of the molded article.
Examples of the crosslinking agent include dimethacrylate compounds, and specific examples include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, and the like.
Examples of the graft crossing agent include allyl compounds, specifically, allyl methacrylate, triallyl cyanurate, triallyl isocyanurate, and the like.

The total of the units derived from the cross-linking agent and the graft cross-linking agent is excellent in the color development of the molded product, and less coagulum (coagulum) during the production of the graft copolymer (F). Of all the units (100% by mass) constituting the acid ester rubbery polymer (E), 0.1 to 5% by mass is preferable, 0.2 to 3% by mass is more preferable, and 0.5 to 2%. More preferred is mass%.
Here, “the sum of the units derived from the crosslinking agent and the unit derived from the graft crossing agent” means the total mass of monomers used in the synthesis of the crosslinked acrylic acid ester rubbery polymer (E) (that is, The total mass of monomers corresponding to the structural units constituting the crosslinked acrylic ester rubber-like polymer (E)) can be calculated from the mass of the crosslinking agent and the graft crossing agent.

The method for producing the crosslinked acrylic ester rubber-like polymer (E) is not particularly limited.
Examples of the method for producing the crosslinked acrylic ester rubbery polymer (E) include emulsion polymerization of a monomer mixture containing (meth) acrylic ester and either or both of a crosslinking agent and a graft crossing agent. To obtain an aqueous dispersion of the crosslinked acrylic ester rubbery polymer (E); an aqueous dispersion of the crosslinked acrylic ester rubbery polymer (E) and an aqueous dispersion of another rubber component. A method of heteroaggregation or co-hypertrophy; a monomer mixture constituting the other in the presence of either an aqueous dispersion of a crosslinked acrylic ester-based rubbery polymer (E) or an aqueous dispersion of another rubber component; Examples include a method of polymerizing and compositing.

Preferable specific examples of the emulsifier used in the emulsion polymerization include sodium or potassium salts of fatty acids (oleic acid, stearic acid, myristic acid, stearic acid, palmitic acid, etc.), sodium lauryl sulfate, sodium N-lauroyl sarcosinate, alkenyl succinic acid Examples include dipotassium, sodium alkyldiphenyl ether disulfonate, and the like, and acid-type emulsifiers or salts thereof having two or more functional groups in one molecule from the viewpoint of further suppressing gas generation during molding of the thermoplastic resin composition (I) Is preferred.
As the acid-type emulsifier having two functional groups in one molecule or a salt thereof, dipotassium alkenyl succinate and sodium alkyldiphenyl ether disulfonate are preferable, and sulfuric acid is added to the crosslinked acrylic ester rubber polymer from an aqueous dispersion. In view of easy coagulation and recovery of (E), dipotassium alkenyl succinate is more preferable.
Specific examples of dipotassium alkenyl succinate include dipotassium octadecenyl succinate, dipotassium heptadecenyl succinate, and dipotassium hexadecenyl succinate.
An emulsifier may be used individually by 1 type and may be used in combination of 2 or more type.

The volume average particle diameter of the crosslinked acrylic ester rubber-like polymer (E) in the aqueous dispersion is 0.05 to 0.18 μm and 0.07 to 0.15 μm from the viewpoint of excellent physical properties of the molded product. Is preferred.
When the volume average particle diameter is smaller than 0.05 μm, the impact resistance of the molded product is inferior.
When the volume average particle diameter is larger than 0.18 μm, the impact resistance and color developability of the molded product are inferior.
Examples of a method for controlling the volume average particle size of the crosslinked acrylic ester rubber-like polymer (E) in the aqueous dispersion include a method for adjusting the type or amount of the emulsifier.

<Vinyl monomer mixture (m2)>
The vinyl monomer mixture (m2) is a monomer mixture containing at least an aromatic vinyl compound and a vinyl cyanide compound.

Examples of the aromatic vinyl compound include styrene, α-methyl styrene, o-, m- or p-methyl styrene, vinyl xylene, pt-butyl styrene, ethyl styrene, and the like. Styrene and α-methylstyrene are preferred from the viewpoint of the fluidity of I), the color developability of the molded product, and the impact resistance.
An aromatic vinyl compound may be used individually by 1 type, and may be used in combination of 2 or more type.
The content of the aromatic vinyl compound is preferably 65 to 82% by mass, more preferably 73 to 80% by mass, and further preferably 75 to 80% by mass in 100% by mass of the vinyl monomer mixture (m2).
When the content of the aromatic vinyl compound is within the above range, the color developability and impact resistance of the molded product are further improved.

Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile.
A vinyl cyanide compound may be used individually by 1 type, and may be used in combination of 2 or more type.
The content of the vinyl cyanide compound is preferably 18 to 35% by mass, more preferably 20 to 27% by mass, and further preferably 20 to 25% by mass in 100% by mass of the vinyl monomer mixture (m2).
When the content of the vinyl cyanide compound is within the above range, the color developability and impact resistance of the molded product are further improved.

The vinyl monomer mixture (m2) may contain, in addition to the aromatic vinyl compound and the vinyl cyanide compound, other monomers copolymerizable therewith within a range not impairing the effects of the present invention.
Other monomers include, for example, methacrylic acid esters (methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-methacrylic acid t- Butyl, amyl methacrylate, isoamyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate, pentyl methacrylate, phenyl methacrylate, etc.), maleimide compounds (N-methyl) Maleimide, N-ethylmaleimide, Nn-propylmaleimide, Ni-propylmaleimide, Nn-butylmaleimide, Ni-butylmaleimide, N-tert-butylmaleimide, N-cycloalkylmaleimide ( -Cyclohexylmaleimide), N-arylmaleimide (N-phenylmaleimide, N-alkyl-substituted phenylmaleimide, N-chlorophenylmaleimide, etc.), N-aralkylmaleimide, etc.), acrylic acid ester (methyl acrylate, ethyl acrylate, acrylic) Propyl acid, butyl acrylate, etc.).
Another monomer may be used individually by 1 type and may be used in combination of 2 or more type.

<Graft copolymer (F)>
The graft copolymer (F) can be obtained by polymerizing the vinyl monomer (m2) in the presence of the cross-linked acrylic ester rubber-like polymer (E).

The graft copolymer (F) is a vinyl monomer mixture (m2) 20 to 80% by mass (provided that the crosslinked acrylic polymer (E) is 20 to 80% by mass in the presence of the crosslinked acrylic ester rubbery polymer (E)). The polymer obtained by polymerizing the acid ester rubber polymer (E) and the vinyl monomer mixture (m2) is preferably 100% by mass), and is preferably a crosslinked acrylate rubber polymer (E And more preferably obtained by polymerizing 25 to 75% by mass of the vinyl monomer mixture (m2) in the presence of 25 to 75% by mass, and the crosslinked acrylic ester rubbery polymer (E) 30. What is obtained by polymerizing 30 to 70% by mass of the vinyl-based monomer mixture (m2) in the presence of to 70% by mass is more preferable.
When the ratio of the crosslinked acrylic acid ester-based rubbery polymer (E) is within the above range, the productivity of the graft copolymer (F) is good, and the color developability and impact resistance of the molded product are further improved. .

The graft copolymer (F) is produced, for example, by emulsion polymerization.
That is, adding a vinyl monomer mixture (m2) to an aqueous dispersion of a crosslinked acrylic ester rubber-like polymer (E) and radically polymerizing the vinyl monomer mixture (m2) in the presence of an emulsifier. Manufactured by.
At this time, various known chain transfer agents may be added in order to control the graft ratio and the molecular weight of the graft component.

Examples of radical polymerization initiators include peroxides, azo-based initiators, redox-based initiators in which an oxidizing agent and a reducing agent are combined, and redox-based initiators from the point that the graft polymerization reaction can be easily controlled. A sulfoxylate-based initiator in which ferrous sulfate-ethylenediaminetetraacetic acid disodium salt-longalite-hydroperoxide is combined is particularly preferable.

As an emulsifier, the emulsifier used in the case of manufacture of a crosslinked acrylate-type rubber-like polymer (E) is mentioned.
The emulsifier contained in the aqueous dispersion of the crosslinked acrylic acid ester rubber polymer (E) is used as it is, and it is not necessary to add an emulsifier at the time of graft polymerization. May be added.

As a method for recovering the graft copolymer (F) from the aqueous dispersion of the graft copolymer (F), the aqueous dispersion is poured into hot water in which a coagulant is dissolved, and coagulated in a slurry state. A method of recovering the graft copolymer (F) by spraying an aqueous dispersion of the graft copolymer (F) in a heated atmosphere (spray drying) Law).

Examples of the coagulant include inorganic acids (sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, etc.), metal salts (calcium chloride, calcium acetate, aluminum sulfate, etc.) and the like.
The coagulant is selected according to the emulsifier used in the polymerization.
That is, when only a sodium or potassium salt of a carboxylic acid such as a sodium or potassium salt of a fatty acid or a sodium or potassium salt of rosin acid is used as an emulsifier, any coagulant may be used.
When an emulsifier exhibiting a stable emulsifying power even in an acidic region such as sodium dodecylbenzenesulfonate is included as an emulsifier, it is necessary to use a metal salt.

As a method of obtaining the dry graft copolymer (F) from the slurry graft copolymer (F), after the emulsifier residue remaining in the slurry is eluted in water by washing, (i) the slurry is Examples include a method of dehydrating with a centrifugal dehydrator or a press dehydrator and further drying with an air flow dryer or the like, and (ii) a method of simultaneously performing dehydration and drying with a press dehydrator or an extruder.
After drying, the graft copolymer (F) is obtained in the form of powder or particles.
Moreover, you may send the graft copolymer (F) discharged | emitted from the press dehydrator or the extruder directly to the extruder or molding machine which manufactures the thermoplastic resin composition (I).

<Polyorganosiloxane (La)>
The polyorganosiloxane (La) is preferably a polyorganosiloxane (La) having a vinyl polymerizable functional group from the viewpoint of impact resistance of the molded product, and is based on the total of the structural units constituting the polyorganosiloxane (La). A silicon atom having 0.3 to 3 mol% of units derived from siloxane having a vinyl polymerizable functional group and 97 to 99.7 mol% of units derived from dimethylsiloxane has 3 or more siloxane bonds. Polyorganosiloxane (La) that is 1 mol% or less with respect to all silicon atoms in polydimethylsiloxane (La) is more preferable.

Examples of dimethylsiloxane include dimethylsiloxane-based cyclic bodies having 3 or more members, and those having 3 to 7 members are preferable.
Specific examples include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane.
Dimethylsiloxane may be used alone or in combination of two or more.

The siloxane having a vinyl polymerizable functional group only needs to have a vinyl polymerizable functional group and can be bonded to dimethylsiloxane via a siloxane bond.
As the siloxane having a vinyl polymerizable functional group, an alkoxysilane compound having a vinyl polymerizable functional group is preferable from the viewpoint of reactivity with dimethylsiloxane.
Specifically, methacryloyloxysiloxane (β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyl) Ethoxydiethylsilane, γ-methacryloyloxypropyldiethoxymethylsilane, δ-methacryloyloxybutyldiethoxymethylsilane, etc.), vinyl siloxane (tetramethyltetravinylcyclotetrasiloxane etc.), p-vinylphenyldimethoxymethylsilane, mercaptosiloxane (Γ-mercaptopropyldimethoxymethylsilane, γ-mercaptopropyltrimethoxysilane, etc.).
One type of siloxane having a vinyl polymerizable functional group may be used alone, or two or more types may be used in combination.

The polyorganosiloxane (La) may have a unit derived from a siloxane-based crosslinking agent as necessary.
Examples of the siloxane crosslinking agent include trifunctional or tetrafunctional silane crosslinking agents such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, and tetrabutoxysilane.

Polyorganosiloxane (La) can be produced as follows.
If necessary, a siloxane-based crosslinking agent is added to a siloxane mixture composed of dimethylsiloxane and a siloxane having a vinyl polymerizable functional group, and emulsified with an emulsifier and water to obtain an aqueous siloxane mixture dispersion.
The aqueous dispersion of the siloxane mixture is atomized using a homomixer that atomizes by a shearing force by high-speed rotation, a homogenizer that atomizes by a jet output from a high-pressure generator, or the like.
It is preferable to use a high-pressure emulsifier such as a homogenizer because the particle size distribution of the polyorganosiloxane (La) becomes small.
The finely divided siloxane mixture aqueous dispersion is added to an acid aqueous solution containing an acid catalyst and polymerized at a high temperature. The reaction liquid is cooled and the polymerization is stopped by neutralizing with an alkaline substance (sodium hydroxide, potassium hydroxide, sodium carbonate, etc.) to obtain an aqueous dispersion of polyorganosiloxane (La).

As the emulsifier, an anionic emulsifier is preferable.
Examples of the anionic emulsifier include sodium alkylbenzene sulfonate, sodium lauryl sulfonate, sodium polyoxyethylene nonylphenyl ether sulfate, and the like, which makes it easy to control the volume average particle diameter of polyorganosiloxane (La). Therefore, sulfonic acid-based emulsifiers (sodium alkylbenzene sulfonate, sodium lauryl sulfonate, etc.) are preferable.
The amount of the emulsifier used is about 0.05 to 20 parts by mass with respect to 100 parts by mass (as solid content) of the siloxane mixture.

Examples of the acid catalyst include sulfonic acids (aliphatic sulfonic acid, aliphatic substituted benzenesulfonic acid, aliphatic substituted naphthalenesulfonic acid, etc.), mineral acids (sulfuric acid, hydrochloric acid, nitric acid, etc.), and polyorganosiloxane (La). Aliphatic substituted benzenesulfonic acid is preferred, and n-dodecylbenzenesulfonic acid is particularly preferred from the viewpoint of excellent stabilization of the aqueous dispersion.
In addition, when n-dodecylbenzene sulfonic acid and mineral acids (sulfuric acid, etc.) are used in combination, the emulsifier used in the aqueous dispersion of polyorganosiloxane (La) suppresses as much as possible the influence of color development on the molded product. Can do.
An acid catalyst may be used individually by 1 type, and may be used in combination of 2 or more type.

The volume average particle diameter of the polyorganosiloxane (La) in the aqueous dispersion is such that the color developability of the molded product is excellent, the viscosity of the aqueous dispersion during the production of the polyorganosiloxane (La), and the coagulum (coagulum). ) Is preferably from 0.01 to 0.09 μm, more preferably from 0.02 to 0.08 μm from the viewpoint of preventing the occurrence.
As a method for controlling the volume average particle diameter of the polyorganosiloxane (La) in the aqueous dispersion, for example, a method described in JP-A-5-279434 can be employed.

<Poly (meth) acrylic acid ester (Lb)>
The poly (meth) acrylic acid ester (Lb) is a copolymer having a unit derived from a (meth) acrylic acid ester and either a unit derived from a crosslinking agent or a unit derived from a graft crossing agent or both. It is.

The total of the unit derived from the crosslinking agent and the unit derived from the graft crossing agent is excellent in the color developability of the molded product, and the coagulum during production of the graft copolymer (M) is reduced. Of all the units (100% by mass) constituting the (meth) acrylate (Lb), 0.1 to 5% by mass is preferable, 0.2 to 3% by mass is more preferable, and 0.5 to 2% by mass Is more preferable.
Here, the “unit derived from the crosslinking agent and the unit derived from the graft crossing agent” means the total mass of the monomers used in the synthesis of the poly (meth) acrylic acid ester (Lb) (ie, poly (meth) acryl It can be calculated from the mass of the crosslinking agent and the graft crossing agent relative to the total mass of the monomer corresponding to the structural unit constituting the acid ester (Lb).

The poly (meth) acrylic acid ester (Lb) can be produced as follows.
The production method of the poly (meth) acrylate ester (Lb) is not particularly limited. For example, a monomer mixture containing (meth) acrylate ester and one or both of a crosslinking agent and a graft crossing agent is used. The method of obtaining the aqueous dispersion of poly (meth) acrylic acid ester (Lb) by emulsion polymerization is mentioned.
Preferable specific examples of the emulsifier used in the emulsion polymerization include sodium or potassium salts of fatty acids (oleic acid, stearic acid, myristic acid, stearic acid, palmitic acid, etc.), sodium lauryl sulfate, sodium N-lauroyl sarcosinate, alkenyl succinic acid Examples include dipotassium, sodium alkyldiphenyl ether disulfonate, and the like, and acid-type emulsifiers or salts thereof having two or more functional groups in one molecule from the viewpoint of further suppressing gas generation during molding of the thermoplastic resin composition (I) Is preferred.
The acid-type emulsifier having two functional groups in one molecule or a salt thereof is preferably dipotassium alkenyl succinate or sodium alkyldiphenyl ether disulfonate. In view of easy coagulation and recovery, dipotassium alkenyl succinate is more preferable.
Specific examples of dipotassium alkenyl succinate include dipotassium octadecenyl succinate, dipotassium heptadecenyl succinate, and dipotassium hexadecenyl succinate.
An emulsifier may be used individually by 1 type and may be used in combination of 2 or more type.

<Composite rubbery polymer (L)>
The composite rubber-like polymer (L) contains polyorganosiloxane (La).
The rubber-like polymer (L) includes a rubber-like polymer composed only of polyorganosiloxane (La), and a composite rubber-like polymer composed of a polymer other than polyorganosiloxane (La) and polyorganosiloxane (La). Etc.
The rubber-like polymer (L) is a composite rubber-like polymer (L1) composed of a polyorganosiloxane (La) and a poly (meth) acrylic acid ester (Lb) from the viewpoint that the effects of the present invention are sufficiently obtained. It is preferable.

The content of the polyorganosiloxane (La) in the rubbery polymer (L) is preferably 1 to 99% by mass, more preferably 2 to 80% by mass with respect to the total mass of the rubbery polymer (L). More preferably, it is 3 to 50% by mass.
When the content of the polyorganosiloxane (La) is within the above range, the impact resistance and color developability of the molded product are further improved.

The content of the polyorganosiloxane (La) in the composite rubbery polymer (L1) is preferably 1 to 99% by mass, more preferably 2 to 80% by mass with respect to the total mass of the composite rubbery polymer (L1). Preferably, 3 to 50% by mass is more preferable.
When the content of the polyorganosiloxane (La) is within the above range, the impact resistance and color developability of the molded product are further improved.

The production method of the composite rubbery polymer (L1) is not particularly limited.
As a method for producing the composite rubber-like polymer (L1), for example, an aqueous dispersion of polyorganosiloxane (La) and an aqueous dispersion of poly (meth) acrylic acid ester (Lb) separately produced are heteroaggregated or Method of co-hypertrophy; Method of forming the other polymer in one of an aqueous dispersion of polyorganosiloxane (La) or an aqueous dispersion of poly (meth) acrylic acid ester (Lb) and combining them In the aqueous dispersion of polyorganosiloxane (La), either (meth) acrylic acid ester and either crosslinking agent or graft crossing agent A method of emulsion polymerization of a monomer mixture containing one or both is preferred.

Preferable specific examples of the emulsifier used in the emulsion polymerization include sodium or potassium salts of fatty acids (oleic acid, stearic acid, myristic acid, stearic acid, palmitic acid, etc.), sodium lauryl sulfate, sodium N-lauroyl sarcosinate, alkenyl succinic acid Examples include dipotassium, sodium alkyldiphenyl ether disulfonate, and the like, and acid-type emulsifiers or salts thereof having two or more functional groups in one molecule from the viewpoint of further suppressing gas generation during molding of the thermoplastic resin composition (I) Is preferred.
The acid-type emulsifier having two functional groups in one molecule or a salt thereof is preferably dipotassium alkenyl succinate or sodium alkyldiphenyl ether disulfonate. In view of easy coagulation and recovery, dipotassium alkenyl succinate is more preferable.
Specific examples of dipotassium alkenyl succinate include dipotassium octadecenyl succinate, dipotassium heptadecenyl succinate, and dipotassium hexadecenyl succinate.
An emulsifier may be used individually by 1 type and may be used in combination of 2 or more type.

The volume average particle diameter of the composite rubber-like polymer (L) and the composite rubber-like polymer (L1) in the aqueous dispersion is 0.05 to 0.18 μm from the viewpoint of excellent physical properties of the molded product. A thickness of 07 to 0.15 μm is preferable.
When the volume average particle diameter is smaller than 0.05 μm, the impact resistance and lubricity of the molded product are inferior.
When the volume average particle diameter is larger than 0.18 μm, the impact resistance, color developability and lubricity of the molded product are inferior.
Examples of the method for controlling the volume average particle diameter of the composite rubber-like polymer (L) and the composite rubber-like polymer (L1) in the aqueous dispersion include a method for adjusting the type or amount of the emulsifier.

<Vinyl monomer mixture (m5)>
The vinyl monomer mixture (m5) is a monomer component containing an arbitrary vinyl monomer. Examples of vinyl monomers include aromatic vinyl compounds, vinyl cyanide compounds, and other monomers copolymerizable therewith.
The vinyl monomer component (m5) is preferably a monomer mixture containing at least an aromatic vinyl compound and a vinyl cyanide compound from the viewpoint that the effects of the present invention are sufficiently obtained.

Examples of the aromatic vinyl compound include styrene, α-methyl styrene, o-, m- or p-methyl styrene, vinyl xylene, pt-butyl styrene, ethyl styrene, and the like. Styrene and α-methylstyrene are preferred from the viewpoint of the fluidity of I), the color developability of the molded product, and the impact resistance.
An aromatic vinyl compound may be used individually by 1 type, and may be used in combination of 2 or more type.
The content of the aromatic vinyl compound is preferably 65 to 82% by mass, more preferably 73 to 80% by mass, and further preferably 75 to 80% by mass in 100% by mass of the vinyl monomer mixture (m5).
When the content of the aromatic vinyl compound is within the above range, the color developability and impact resistance of the molded product are further improved.

Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile.
A vinyl cyanide compound may be used individually by 1 type, and may be used in combination of 2 or more type.
The content of the vinyl cyanide compound is preferably 18 to 35% by mass, more preferably 20 to 27% by mass, and further preferably 20 to 25% by mass in 100% by mass of the vinyl monomer mixture (m5).
When the content of the vinyl cyanide compound is within the above range, the color developability and impact resistance of the molded product are further improved.

The vinyl-based monomer mixture (m5) containing an aromatic vinyl compound and a vinyl cyanide compound includes, in addition to the aromatic vinyl compound and the vinyl cyanide compound, other monomers copolymerizable therewith. You may include in the range which does not impair the effect of.
Other monomers include, for example, methacrylic acid esters (methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-methacrylic acid t- Butyl, amyl methacrylate, isoamyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate, pentyl methacrylate, phenyl methacrylate, etc.), maleimide compounds (N-methyl) Maleimide, N-ethylmaleimide, Nn-propylmaleimide, Ni-propylmaleimide, Nn-butylmaleimide, Ni-butylmaleimide, N-tert-butylmaleimide, N-cycloalkylmaleimide ( -Cyclohexylmaleimide), N-arylmaleimide (N-phenylmaleimide, N-alkyl-substituted phenylmaleimide, N-chlorophenylmaleimide, etc.), N-aralkylmaleimide, etc.), acrylic acid ester (methyl acrylate, ethyl acrylate, acrylic) Propyl acid, butyl acrylate, etc.).
Another monomer may be used individually by 1 type and may be used in combination of 2 or more type.

<Graft copolymer (M)>
The graft copolymer (M) is obtained by polymerizing the vinyl monomer (m5) in the presence of the composite rubber-like polymer (L).

The graft copolymer (M) is 20 to 80% by mass of the vinyl monomer mixture (m5) in the presence of 20 to 80% by mass of the composite rubbery polymer (L). L) and a vinyl monomer mixture (m5) are preferably obtained by polymerizing 100% by mass), and in the presence of 25 to 75% by mass of the composite rubber-like polymer (L), vinyl More preferred is a polymer obtained by polymerizing 25 to 75% by mass of the monomeric monomer mixture (m5). In the presence of 30 to 70% by mass of the composite rubber-like polymer (L), a vinyl monomer mixture ( m5) What is obtained by polymerizing 30 to 70% by mass is more preferable.
When the ratio of the composite rubber-like polymer (L) is within the above range, the productivity of the graft copolymer (M) is good, and the color developability and impact resistance of the molded product are further improved.

The graft copolymer (M) is produced, for example, by a radical polymerization initiator and emulsion polymerization.
That is, it is produced by adding a vinyl monomer mixture (m5) to an aqueous dispersion of a composite rubber-like polymer (L) and radically polymerizing the vinyl monomer mixture (m5) in the presence of an emulsifier. .
At this time, various known chain transfer agents may be added in order to control the graft ratio and the molecular weight of the graft component.

As an emulsifier, the emulsifier used in the case of manufacture of a composite rubber-like polymer (L) is mentioned.
The emulsifier contained in the aqueous dispersion of the composite rubber polymer (L) is used as it is, and it is not necessary to add an emulsifier at the time of graft polymerization, or an emulsifier may be added at the time of graft polymerization as necessary. Good.

As a method for recovering the graft copolymer (M) from the aqueous dispersion of the graft copolymer (M), the aqueous dispersion is poured into hot water in which a coagulant is dissolved, and coagulated in a slurry state. A method of recovering the graft copolymer (M) by spraying an aqueous dispersion of the graft copolymer (M) in a heated atmosphere (spray drying). Law).

As a method for obtaining a dry graft copolymer (M) from a slurry graft copolymer (M), after the emulsifier residue remaining in the slurry is eluted in water by washing, (i) the slurry is Examples include a method of dehydrating with a centrifugal dehydrator or a press dehydrator and further drying with an airflow dryer or the like, and (ii) a method of simultaneously performing dehydration and drying with a press dehydrator or an extruder.
After drying, the graft copolymer (M) is obtained in the form of powder or particles.
Moreover, you may send the graft copolymer (M) discharged | emitted from the press dehydrator or the extruder directly to the extruder or molding machine which manufactures the thermoplastic resin composition (I).

<Vinyl monomer mixture (m3)>
The vinyl monomer mixture (m3) contains at least a methacrylic acid ester as an essential component, and is a maleimide compound, an aromatic vinyl compound, an acrylic acid ester, and other vinyl monomers copolymerizable with the methacrylic acid ester. Is a monomer mixture containing as an optional component.

The content of the methacrylic acid ester is preferably 50 to 100% by mass in 100% by mass of the vinyl monomer mixture (m3) from the viewpoint of scratch resistance and color developability of the molded product.
If the content of the methacrylic acid ester is in the range of 50 to 94% by mass, the content of the maleimide compound is 5 to 49% by mass, and the content of the aromatic vinyl compound is 1 to 45% by mass, Scratch resistance, color development, impact resistance, and heat resistance are even better.

Examples of the methacrylic acid ester include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, amyl methacrylate, Examples include isoamyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate, penzyl methacrylate, phenyl methacrylate, and the like. From the viewpoint of superiority, at least one of methyl methacrylate and ethyl methacrylate is preferable. A methacrylic acid ester may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of maleimide compounds include N-alkylmaleimide (N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, Ni-propylmaleimide, Nn-butylmaleimide, Ni-butylmaleimide). Nt-butylmaleimide), N-cycloalkylmaleimide (N-cyclohexylmaleimide, etc.), N-arylmaleimide (N-phenylmaleimide, N-alkyl-substituted phenylmaleimide, N-chlorophenylmaleimide, etc.), etc. N-arylmaleimide is preferred, and N-phenylmaleimide is particularly preferred from the viewpoint that the heat resistance and impact resistance of the molded product are further improved.
A maleimide type compound may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of the aromatic vinyl compound include styrene, α-methyl styrene, o-, m- or p-methyl styrene, vinyl xylene, pt-butyl styrene, ethyl styrene, and the like. Styrene and α-methylstyrene are preferred from the viewpoint of further excellent impact resistance. An aromatic vinyl compound may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of the acrylate ester include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate and the like, and methyl acrylate is preferable from the viewpoint of further improving the heat resistance and impact resistance of the molded product. One kind of acrylic acid ester may be used alone, or two or more kinds may be used in combination.

Examples of other vinyl monomers include vinyl cyanide compounds (acrylonitrile, methacrylonitrile, etc.). Another vinyl-type monomer may be used individually by 1 type, and may be used in combination of 2 or more type.

<Methacrylate ester resin (G)>
The methacrylic ester resin (G) can be obtained by polymerizing the vinyl monomer mixture (m3).
The polymerization method is not limited. Examples of the polymerization method include known polymerization methods (emulsion polymerization method, suspension polymerization method, solution polymerization method, etc.).

As a method for producing a methacrylate ester resin (G) by an emulsion polymerization method, for example, in the presence of water, a vinyl monomer mixture (m3), an emulsifier, a polymerization initiator, and a chain transfer agent are charged in a reactor, A method of heating and polymerizing and recovering the methacrylic ester resin (G) from the aqueous dispersion containing the methacrylic ester resin (G) by a precipitation method is mentioned.
Examples of the emulsifier include usual emulsion polymerization emulsifiers (potassium rosinate, sodium alkylbenzenesulfonate, etc.).
Examples of the polymerization initiator include organic and inorganic peroxide initiators.
Examples of the chain transfer agent include mercaptans, α-methylstyrene dimer, terpenes and the like.
As the precipitation method, a method similar to that used when recovering the graft copolymer (D) from the aqueous dispersion can be employed.

Examples of the method for producing a methacrylate ester resin (G) by suspension polymerization include, for example, a vinyl monomer mixture (m3), a suspending agent, a suspending aid, a polymerization initiator, and a chain transfer agent in a reactor. And then polymerizing by heating, and dehydrating and drying the slurry to recover the methacrylic ester resin (G).
Examples of the suspending agent include tricalcium phosphite and polyvinyl alcohol.
Examples of the suspension aid include sodium alkylbenzene sulfonate.
Examples of the polymerization initiator include organic peroxides.
Examples of the chain transfer agent include mercaptans, α-methylstyrene dimer, terpenes and the like.

A methacrylic ester resin (G) may be used individually by 1 type, and may be used in combination of 2 or more type.

<Vinyl monomer mixture (m4)>
The vinyl monomer mixture (m4) is a monomer mixture containing at least an aromatic vinyl compound and a vinyl cyanide compound.

Examples of the aromatic vinyl compound include styrene, α-methyl styrene, o-, m- or p-methyl styrene, vinyl xylene, pt-butyl styrene, ethyl styrene, and the like. Styrene and α-methylstyrene are preferred from the viewpoint of the fluidity of I), the color developability of the molded product, and the impact resistance. An aromatic vinyl compound may be used individually by 1 type, and may be used in combination of 2 or more type.
The content of the aromatic vinyl compound is preferably 15 to 95% by mass in 100% by mass of the vinyl monomer mixture (m4). When the content of the aromatic vinyl compound is within the above range, the impact resistance of the molded product is further improved.

Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. A vinyl cyanide compound may be used individually by 1 type, and may be used in combination of 2 or more type.
The content of the vinyl cyanide compound is preferably 5 to 85% by mass in 100% by mass of the vinyl monomer mixture (m4). When the content of the vinyl cyanide compound is within the above range, the impact resistance of the molded product is further improved.

The vinyl monomer mixture (m4) may contain a methacrylic acid ester and a maleimide compound as necessary.
Examples of the methacrylic acid ester and the maleimide compound include those exemplified in the vinyl monomer mixture (m3).

<Styrene copolymer (H)>
The styrene copolymer (H) is obtained by polymerizing a vinyl monomer mixture (m4) containing an aromatic vinyl compound and a vinyl cyanide compound.

The polymerization method is not limited. Examples of the polymerization method include known polymerization methods (emulsion polymerization method, suspension polymerization method, bulk polymerization method, solution polymerization method, etc.). From the viewpoint of heat resistance of the molded product, suspension polymerization method and bulk polymerization method are available. preferable.

<Other thermoplastic resins>
Other thermoplastic resins include, for example, polycarbonate, polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyvinyl chloride, polystyrene, polyacetal, modified polyphenylene ether (modified PPE), ethylene-vinyl acetate copolymer, poly Examples include arylate, liquid crystal polyester, polyethylene, polypropylene, fluororesin, and polyamide (nylon).

<Various additives>
Examples of various additives include antioxidants, lubricants, processing aids, pigments, fillers, silicone oils, paraffin oils, and the like.

<Content of each component>
In the thermoplastic resin composition (I) of the third aspect of the present invention, the content of the graft copolymer (D) is such that the graft copolymer (D), the methacrylate ester resin (G), and the styrene copolymer The total content is preferably 10 to 30% by mass, more preferably 15 to 25% by mass, based on 100% by mass with the combined (H). If the content of the graft copolymer (D) is within the above range, physical properties such as fluidity of the thermoplastic resin composition (I), scratch resistance, impact resistance, color development, and heat resistance of the molded product. Excellent balance.

In the thermoplastic resin composition (I) of the third aspect of the present invention, the content of the methacrylic ester resin (G) is such that the graft copolymer (D), the methacrylic ester resin (G), and the styrene copolymer 30 to 90% by mass is preferable among 100% by mass in total with the combined (H), and 35 to 85% by mass is more preferable. If the content of the methacrylic ester resin (G) is within the above range, the physical properties of the thermoplastic resin composition (I) such as fluidity, scratch resistance, impact resistance, color development, and heat resistance of the molded product. Excellent balance.

In the thermoplastic resin composition (I) of the third aspect of the present invention, the content of the styrene copolymer (H) is such that the graft copolymer (D), the methacrylate ester resin (G), and the styrene copolymer. It is preferably 0 to 40% by mass in 100% by mass with respect to the polymer (H), and 1 to 40% by mass from the viewpoint of fluidity of the thermoplastic resin composition (I), impact resistance of the molded product, and heat resistance. Is more preferable.

<Content of each component>
In the thermoplastic resin composition (I) of the fourth aspect of the present invention, the proportion of the ethylene / α-olefin copolymer (A) or the crosslinked ethylene / α-olefin copolymer (C) is ethylene / α-olefin. 15 to 85% by mass of the total (100% by mass) of the olefin copolymer (A), the crosslinked ethylene / α-olefin copolymer (C) and the crosslinked acrylic acid ester rubbery polymer (E) 30 to 70% by mass is preferable.
In the thermoplastic resin composition (I) of the fourth aspect of the present invention, the proportion of the crosslinked acrylic ester rubber-like polymer (E) is such that the ethylene / α-olefin copolymer (A), the crosslinked ethylene / α -Of the total (100% by mass) of the olefin copolymer (C) and the crosslinked acrylic acid ester-based rubbery polymer (E), it is 85 to 15% by mass, preferably 30 to 70% by mass.
In the thermoplastic resin composition (I) of the fourth aspect of the present invention, the ratio of the ethylene / α-olefin copolymer (A) or the crosslinked ethylene / α-olefin copolymer (C) and the crosslinked acrylic ester system When the ratio of the rubber-like polymer (E) is within the above range, impact resistance can be expressed with a small rubber content, and further, scratch resistance and color developability are excellent.

In the thermoplastic resin composition (I) of the fourth aspect of the present invention, an ethylene / α-olefin copolymer (A), a crosslinked ethylene / α-olefin copolymer (C), and a crosslinked acrylic ester rubber The total content (rubber content) of the polymer (E) is preferably 5 to 30% by mass and more preferably 10 to 25% by mass in 100% by mass of the thermoplastic resin composition (I).
When the rubber content is within the above range, the fluidity of the thermoplastic resin composition (I), the impact strength of the molded product, the scratch resistance, and the color developability are further improved.

In the thermoplastic resin composition (I) of the fourth aspect of the present invention, the total content of the graft copolymer (D) and the graft copolymer (F) is as follows. The total content of the polymer (F), the methacrylic ester resin (G) and the styrene copolymer (H) is preferably 5 to 40% by mass, more preferably 10 to 30% by mass.
If the total content of the graft copolymer (D) and the graft copolymer (F) is within the above range, the fluidity of the thermoplastic resin composition (I), the scratch resistance of the molded product, and the impact resistance Excellent balance of physical properties such as property, color development and heat resistance.

In the thermoplastic resin composition (I) of the fourth aspect of the present invention, the content of the methacrylic ester resin (G) is as follows: graft copolymer (D), graft copolymer (F), methacrylic ester resin Of the total 100% by mass of (G) and the styrene copolymer (H), 95 to 60% by mass is preferable, and 90 to 70% by mass is more preferable.
If the content of the methacrylic ester resin (G) is within the above range, the properties of the thermoplastic resin composition (I) such as fluidity, scratch resistance, impact resistance, color development, and heat resistance of the molded product. Excellent balance.

In the thermoplastic resin composition (I) of the fourth aspect of the present invention, the content of the styrenic copolymer (H) is as follows: graft copolymer (D), graft copolymer (F), methacrylate ester The content is preferably 0 to 40% by mass in 100% by mass of the resin (G) and the styrene-based copolymer (H), and the fluidity of the thermoplastic resin composition (I), the impact resistance of the molded product, and the heat resistance Therefore, 1 to 40% by mass is more preferable.

<Volume average particle diameter>
In the thermoplastic resin composition (I) of the fourth aspect of the present invention, the ethylene / α-olefin copolymer (A) contained in the graft copolymer (D) in the thermoplastic resin composition (I) or The volume average particle diameter of the crosslinked ethylene / α-olefin copolymer (C) is 0.2 to 0.6 μm, preferably 0.3 to 0.5 μm.
When the volume average particle diameter is smaller than 0.2 μm, the impact resistance of the molded product is inferior.
When the volume average particle diameter is larger than 0.6 μm, the impact resistance and color developability of the molded product are inferior.
If the volume average particle diameter of the ethylene / α-olefin copolymer (A) or the crosslinked ethylene / α-olefin copolymer (C) is 0.3 μm to 0.5 μm, the impact resistance and color developability of the molded product Is even better.
The volume average particle diameter of the ethylene / α-olefin copolymer (A) or the crosslinked ethylene / α-olefin copolymer (C) dispersed in the aqueous dispersion is as it is in the thermoplastic resin composition (I). The fact that the volume average particle diameter of the ethylene / α-olefin copolymer (A) and the crosslinked ethylene / α-olefin copolymer (C) is confirmed by image processing of electron micrographs.

In the thermoplastic resin composition (I) of the fourth aspect of the present invention, the crosslinked acrylic ester rubber-like polymer (E) contained in the graft copolymer (F) in the thermoplastic resin composition (I). The volume average particle diameter of is 0.05 to 0.18 μm, preferably 0.07 to 0.15 μm.
When the volume average particle diameter is smaller than 0.05 μm, the impact resistance of the molded product is inferior.
When the volume average particle diameter is larger than 0.18 μm, the impact resistance and color developability of the molded product are inferior.
The volume average particle diameter of the crosslinked acrylate rubber polymer (E) dispersed in the aqueous dispersion is the same as that of the crosslinked acrylate rubber polymer (E) in the thermoplastic resin composition (I). It is confirmed by image processing of an electron micrograph that the volume average particle diameter is shown.

<Content of each component>
In the thermoplastic resin composition (I) of the fifth aspect of the present invention, the ratio of the ethylene / α-olefin copolymer (A) or the crosslinked ethylene / α-olefin copolymer (C) is ethylene / α-olefin. Of the total (100% by mass) of the olefin copolymer (A), the crosslinked ethylene / α-olefin copolymer (C) and the composite rubber-like polymer (L), 15 to 85% by mass, 30 to 70% Mass% is preferred.
In the thermoplastic resin composition (I) of the fifth aspect of the present invention, the proportion of the composite rubber-like polymer (L) is such that the ethylene / α-olefin copolymer (A), the crosslinked ethylene / α-olefin copolymer Of the total (100% by mass) of the combined polymer (C) and the composite rubber-like polymer (L), it is 85 to 15% by mass, preferably 30 to 70% by mass.
The ratio of the ethylene / α-olefin copolymer (A) or the crosslinked ethylene / α-olefin copolymer (C) in the thermoplastic resin composition (I) of the fifth aspect of the present invention and the composite rubber-like polymer When the ratio of (L) is within the above range, impact resistance can be exhibited with a small rubber content, and further, scratch resistance, color developability, and lubricity are excellent.

In the thermoplastic resin composition of the fifth aspect of the present invention, the total of the ethylene / α-olefin copolymer (A), the crosslinked ethylene / α-olefin copolymer (C) and the composite rubber-like polymer (L) The content (rubber content) is preferably 5 to 30% by mass, more preferably 10 to 25% by mass in 100% by mass of the thermoplastic resin composition (I).
When the rubber content is within the above range, the fluidity of the thermoplastic resin composition (I), the impact strength of the molded product, the lubricity, the scratch resistance, and the color developability are further improved.

In the thermoplastic resin composition (I) of the fifth aspect of the present invention, the total content of the graft copolymer (D) and the graft copolymer (M) is as follows. The total amount of the polymer (M), the methacrylic ester resin (G) and the styrene copolymer (H) is preferably 5 to 40% by mass, more preferably 10 to 30% by mass.
If the total content of the graft copolymer (D) and the graft copolymer (M) is within the above range, the fluidity of the thermoplastic resin composition (I), the scratch resistance of the molded product, and the impact resistance Excellent balance of physical properties such as property, color developability, lubricity and heat resistance.

In the thermoplastic resin composition (I) of the fifth aspect of the present invention, the content of the methacrylic ester resin (G) is as follows: graft copolymer (D), graft copolymer (M), methacrylic ester resin Of the total 100% by mass of (G) and the styrene copolymer (H), 95 to 60% by mass is preferable, and 90 to 70% by mass is more preferable.
If the content of the methacrylic ester resin (G) is within the above range, the flowability of the thermoplastic resin composition (I), scratch resistance, impact resistance, color development, lubricity, and heat resistance of the molded product. Excellent physical property balance.

In the thermoplastic resin composition (I) of the fifth aspect of the present invention, the content of the styrene copolymer (H) is as follows: graft copolymer (D), graft copolymer (M), methacrylate ester The content is preferably 0 to 40% by mass in 100% by mass of the resin (G) and the styrene-based copolymer (H), and the fluidity of the thermoplastic resin composition (I), the impact resistance of the molded product, and the heat resistance Therefore, 1 to 40% by mass is more preferable.

<Volume average particle diameter>
In the thermoplastic resin composition (I) of the fifth aspect of the present invention, the ethylene / α-olefin copolymer (A) contained in the graft copolymer (D) in the thermoplastic resin composition (I) or The volume average particle diameter of the crosslinked ethylene / α-olefin copolymer (C) is 0.2 to 0.6 μm, preferably 0.3 to 0.5 μm.
When the volume average particle diameter is smaller than 0.2 μm, the impact resistance and lubricity of the molded product are inferior.
When the volume average particle diameter is larger than 0.6 μm, the impact resistance, color developability and lubricity of the molded product are inferior.
If the volume average particle diameter of the ethylene / α-olefin copolymer (A) or the crosslinked ethylene / α-olefin copolymer (C) is 0.3 μm to 0.5 μm, the impact resistance and color developability of the molded product Is even better. The volume average particle diameter of the ethylene / α-olefin copolymer (A) or the crosslinked ethylene / α-olefin copolymer (C) dispersed in the aqueous dispersion is as it is in the thermoplastic resin composition (I). The fact that the volume average particle diameter of the ethylene / α-olefin copolymer (A) and the crosslinked ethylene / α-olefin copolymer (C) is confirmed by image processing of electron micrographs.

Volume average particles of composite rubber-like polymer (L) contained in graft copolymer (M) in thermoplastic resin composition (I) in thermoplastic resin composition (I) of the fifth aspect of the present invention The diameter is 0.05 to 0.18 μm, preferably 0.07 to 0.15 μm.
When the volume average particle diameter is smaller than 0.05 μm, the impact resistance and lubricity of the molded product are inferior.
When the volume average particle diameter is larger than 0.18 μm, the impact resistance, color developability and lubricity of the molded product are inferior.
The volume average particle diameter of the composite rubber-like polymer (L) dispersed in the aqueous dispersion indicates the volume average particle diameter of the composite rubber-like polymer (L) in the thermoplastic resin composition (I) as it is. Is confirmed by image processing of electron micrographs.

<Method for producing thermoplastic resin composition (I)>
The thermoplastic resin composition (I) of the second aspect is obtained by mixing the graft copolymer (D) in the first aspect of the present invention and the hard component (J) described above.
Specifically, it is easily produced by mixing the graft copolymer (D) and the hard component (J) with various additives as required.
Moreover, you may pelletize with an extruder, a Banbury mixer, a kneading roll etc. as needed.

Although there is no restriction | limiting in particular regarding content of the graft copolymer (D) contained in a thermoplastic resin composition (I), With respect to a total of 100 mass parts of a graft copolymer (D) and a hard component (J), It is preferable to adjust the content of the graft copolymer (D) to be 0.1 to 99 parts by mass.

The thermoplastic resin composition (I) according to the third aspect of the present invention comprises a graft copolymer (D), a methacrylic ester resin (G), and a styrene copolymer (H) as required. It can be obtained by mixing thermoplastic resin, various additives and the like. You may pelletize with an extruder, a Banbury mixer, a kneading roll, etc.

The thermoplastic resin composition (I) in the fourth aspect of the present invention comprises a graft copolymer (D), a graft copolymer (F), a methacrylic ester resin (G), and a styrenic copolymer (H). Is obtained by mixing.

The thermoplastic resin composition (I) in the fifth aspect of the present invention comprises a graft copolymer (D), a graft copolymer (M), a methacrylic ester resin (G), and a styrenic copolymer (H). Is obtained by mixing.

<Effect>
As described above, the thermoplastic resin composition (I) according to the second aspect of the present invention contains the graft copolymer (D) according to the first aspect of the present invention and thus has excellent fluidity and scratch resistance. A molded product excellent in stickiness, impact resistance, glossiness, and color development can be obtained.

In the thermoplastic resin composition (I) according to the third aspect of the present invention described above, the ethylene / α-olefin having a mass average molecular weight (Mw) and a molecular weight distribution (Mw / Mn) within specific ranges. The vinyl monomer mixture (m1) is polymerized in the presence of the copolymer (A) or the crosslinked ethylene / α-olefin copolymer (C) obtained by crosslinking the ethylene / α-olefin copolymer (A). The resulting graft copolymer (D) and methacrylic ester resin (G) have good fluidity and are excellent in scratch resistance, gloss, color development, and impact resistance. Goods can be obtained. Moreover, even if heat resistance is imparted to the molded article, impact resistance is not impaired.

In the thermoplastic resin composition (I) according to the fourth aspect of the present invention described above, the ethylene / α-olefin having a mass average molecular weight (Mw) and a molecular weight distribution (Mw / Mn) within specific ranges. The vinyl monomer mixture (m1) is polymerized in the presence of the copolymer (A) or the crosslinked ethylene / α-olefin copolymer (C) obtained by crosslinking the ethylene / α-olefin copolymer (A). Graft copolymer obtained by polymerizing the vinyl monomer mixture (m2) in the presence of the graft copolymer (D) obtained; and a crosslinked acrylic ester rubber-like polymer (E) And (E) a methacrylate ester resin (G); an ethylene / α-olefin copolymer (A) or a crosslinked ethylene / α-olefin copolymer (C) in the thermoplastic resin composition (I) And cross-linked acrylic ester Rubber-based polymer (E) has a specific volume average particle size; ethylene / α-olefin copolymer (A) or crosslinked ethylene / α-olefin copolymer in thermoplastic resin composition (I) Since the blend (C) and the cross-linked acrylic ester rubber polymer (E) are in a specific ratio, a molded product having good flowability and excellent scratch resistance, color development and impact resistance. Obtainable.
Moreover, even if heat resistance is imparted to the molded article, impact resistance is not impaired.

In the thermoplastic resin composition (I) according to the fifth aspect of the present invention described above, the ethylene / α-olefin having a mass average molecular weight (Mw) and a molecular weight distribution (Mw / Mn) within specific ranges. The vinyl monomer mixture (m1) is polymerized in the presence of the copolymer (A) or the crosslinked ethylene / α-olefin copolymer (C) obtained by crosslinking the ethylene / α-olefin copolymer (A). Obtained by polymerizing the vinyl-based monomer mixture (m5) in the presence of the graft copolymer (D) thus obtained; and the composite rubber-like polymer (L) containing the polyorganosiloxane (La). A graft copolymer (M); and a methacrylate ester resin (G); an ethylene / α-olefin copolymer (A) or a crosslinked ethylene / α-olefin copolymer in the thermoplastic resin composition (I) Combined (C) and composite The rubber-like polymer (L) has a specific volume average particle size; the ethylene / α-olefin copolymer (A) or the crosslinked ethylene / α-olefin copolymer (A) in the thermoplastic resin composition (I) ( Since C) and the composite rubber-like polymer (L) are in a specific ratio, it is possible to obtain a molded article having good flowability and excellent scratch resistance, color development, impact resistance, and lubricity. it can.
Moreover, even if heat resistance is imparted to the molded article, impact resistance is not impaired.

"Molding"
The molded article of the present invention is obtained by molding the thermoplastic resin composition (I) of the second aspect, third aspect, fourth aspect or fifth aspect of the present invention by a known molding method. It is done.
Examples of the molding method include injection molding, press molding, extrusion molding, vacuum molding, and blow molding.
Applications of molded products include vehicle interior parts, vehicle exterior parts, office equipment, home appliances, building materials, and the like.

In the molded product according to the sixth aspect of the present invention described above, since the thermoplastic resin composition (I) of the present invention is used, scratch resistance, gloss, color development, impact resistance, lubrication Excellent in properties. Moreover, in the third aspect of the present invention, if a methacrylic ester resin (G) having a specific copolymer composition or a styrene copolymer (H) is used, the heat resistance is excellent. . Further, in the fourth aspect of the present invention, if a methacrylic ester resin (G) having a specific copolymer composition or a styrene copolymer (H) is used, the heat resistance is also excellent. . Further, in the fifth aspect of the present invention, if a methacrylic ester resin (G) having a specific copolymer composition or a styrene copolymer (H) is used, the heat resistance is excellent. .
Such molded products can be applied to uses such as vehicle interior parts, vehicle exterior parts, office equipment, home appliances, and building materials.

The graft copolymer (D) in the first embodiment of the present invention has a mass average molecular weight (Mw) of 26 × 10 ⁴ to 32 × 10 ⁴ and a molecular weight distribution (Mw / Mn) of 1.9 to 2. In the presence of the ethylene / α-olefin copolymer (A) 5 or the cross-linked ethylene / α-olefin copolymer (C) obtained by crosslinking the ethylene / α-olefin copolymer (A). A graft copolymer obtained by polymerizing a vinyl monomer mixture (m1) containing a vinyl compound and a vinyl cyanide compound is preferred.

The graft copolymer (D) in the first embodiment of the present invention has a mass average molecular weight (Mw) of 26 × 10 ⁴ to 32 × 10 ⁴ and a molecular weight distribution (Mw / Mn) of 1.9 to 2. In the presence of the crosslinked ethylene / α-olefin copolymer (C) obtained by crosslinking the ethylene / α-olefin copolymer (A), a vinyl-based monomer containing an aromatic vinyl compound and a vinyl cyanide compound is used. A graft copolymer obtained by polymerizing a monomer mixture (m1), wherein the crosslinked ethylene / α-olefin copolymer (C) has a gel content of the crosslinked ethylene / α-olefin copolymer. It is preferably 45 to 65% by mass relative to the total mass of (C).

The graft copolymer (D) in the first embodiment of the present invention has a mass average molecular weight (Mw) of 26 × 10 ⁴ to 32 × 10 ⁴ and a molecular weight distribution (Mw / Mn) of 1.9 to 2. In the presence of a crosslinked ethylene / α-olefin copolymer (C) obtained by crosslinking the ethylene / α-olefin copolymer (A), a vinyl-based monomer containing an aromatic vinyl compound and a vinyl cyanide compound is prepared. A graft copolymer obtained by polymerizing a monomer mixture (m1), wherein the crosslinked ethylene / α-olefin copolymer (C) has a gel content of the crosslinked ethylene / α-olefin copolymer. The ethylene / α-olefin copolymer (A) is preferably an ethylene / propylene copolymer in an amount of 45 to 65% by mass based on the total mass of (C).

The graft copolymer (D) in the first embodiment of the present invention has a mass average molecular weight (Mw) of 26 × 10 ⁴ to 32 × 10 ⁴ and a molecular weight distribution (Mw / Mn) of 1.9 to 2. In the presence of the crosslinked ethylene / α-olefin copolymer (C) obtained by crosslinking the ethylene / α-olefin copolymer (A), a vinyl-based monomer containing an aromatic vinyl compound and a vinyl cyanide compound is used. A graft copolymer obtained by polymerizing a monomer mixture (m1), wherein the crosslinked ethylene / α-olefin copolymer (C) has a gel content of the crosslinked ethylene / α-olefin copolymer. The ethylene / α-olefin copolymer (A) is an ethylene / propylene copolymer, and the ethylene / α-olefin copolymer is 45 to 65% by mass with respect to the total mass of (C). (A) Ethylene The unit content is preferably 45 to 65% by mass with respect to the total mass of the constituent units constituting the ethylene / α-olefin copolymer (A).

The graft copolymer (D) in the first embodiment of the present invention has a mass average molecular weight (Mw) of 26 × 10 ⁴ to 32 × 10 ⁴ and a molecular weight distribution (Mw / Mn) of 1.9 to 2. In the presence of the crosslinked ethylene / α-olefin copolymer (C) obtained by crosslinking the ethylene / α-olefin copolymer (A), a vinyl-based monomer containing an aromatic vinyl compound and a vinyl cyanide compound is used. A graft copolymer obtained by emulsion polymerization of a monomer mixture (m1), wherein the crosslinked ethylene / α-olefin copolymer (C) has a gel content of the crosslinked ethylene / α-olefin copolymer The ethylene / α-olefin copolymer (A) is an ethylene / propylene copolymer, and the ethylene / α-olefin copolymer is 45 to 65% by mass based on the total mass of the polymer (C). Of the polymer (A) The ethylene unit content is preferably 45 to 65% by mass with respect to the total mass of the constituent units constituting the ethylene / α-olefin copolymer (A).

The thermoplastic resin composition (I) according to the second aspect of the present invention includes a graft copolymer (D) and a styrene-based copolymer (H), and the graft copolymer (D) has a mass. An ethylene / α-olefin copolymer (A) having an average molecular weight (Mw) of 26 × 10 ⁴ to 32 × 10 ⁴ and a molecular weight distribution (Mw / Mn) of 1.9 to 2.5 or the ethylene / Vinyl monomer mixture (m1) containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of a crosslinked ethylene / α-olefin copolymer (C) obtained by crosslinking the α-olefin copolymer (A) A graft copolymer obtained by polymerizing is preferred.

The thermoplastic resin composition (I) according to the second aspect of the present invention includes a graft copolymer (D) and a styrene-based copolymer (H), and the graft copolymer (D) has a mass. Crosslinking the ethylene / α-olefin copolymer (A) having an average molecular weight (Mw) of 26 × 10 ⁴ to 32 × 10 ⁴ and a molecular weight distribution (Mw / Mn) of 1.9 to 2.5 A graft copolymer obtained by polymerizing a vinyl monomer mixture (m1) containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of the crosslinked ethylene / α-olefin copolymer (C). The gel content of the crosslinked ethylene / α-olefin copolymer (C) is 45 to 65% by mass based on the total mass of the crosslinked ethylene / α-olefin copolymer (C). preferable.

The thermoplastic resin composition (I) according to the second aspect of the present invention includes a graft copolymer (D) and a styrene-based copolymer (H), and the graft copolymer (D) has a mass. Crosslinking the ethylene / α-olefin copolymer (A) having an average molecular weight (Mw) of 26 × 10 ⁴ to 32 × 10 ⁴ and a molecular weight distribution (Mw / Mn) of 1.9 to 2.5 A graft copolymer obtained by polymerizing a vinyl monomer mixture (m1) containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of the crosslinked ethylene / α-olefin copolymer (C). The gel content of the crosslinked ethylene / α-olefin copolymer (C) is 45 to 65% by mass with respect to the total mass of the crosslinked ethylene / α-olefin copolymer (C), The ethylene / α-olefin copolymer (A It is preferred but an ethylene-propylene copolymer.

The thermoplastic resin composition (I) according to the second aspect of the present invention includes a graft copolymer (D) and a styrene-based copolymer (H), and the graft copolymer (D) has a mass. Crosslinking the ethylene / α-olefin copolymer (A) having an average molecular weight (Mw) of 26 × 10 ⁴ to 32 × 10 ⁴ and a molecular weight distribution (Mw / Mn) of 1.9 to 2.5 A graft copolymer obtained by polymerizing a vinyl monomer mixture (m1) containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of the crosslinked ethylene / α-olefin copolymer (C). The gel content of the crosslinked ethylene / α-olefin copolymer (C) is 45 to 65% by mass with respect to the total mass of the crosslinked ethylene / α-olefin copolymer (C), The ethylene / α-olefin copolymer (A Is an ethylene / propylene copolymer, and the content of ethylene units in the ethylene / α-olefin copolymer (A) is the total of the structural units constituting the ethylene / α-olefin copolymer (A). It is preferably 45 to 65% by mass relative to the mass.

The thermoplastic resin composition (I) according to the second aspect of the present invention includes a graft copolymer (D) and a styrene-based copolymer (H), and the graft copolymer (D) has a mass. Crosslinking the ethylene / α-olefin copolymer (A) having an average molecular weight (Mw) of 26 × 10 ⁴ to 32 × 10 ⁴ and a molecular weight distribution (Mw / Mn) of 1.9 to 2.5 Graft copolymer obtained by emulsion polymerization of a vinyl monomer mixture (m1) containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of the crosslinked ethylene / α-olefin copolymer (C) The gel content of the crosslinked ethylene / α-olefin copolymer (C) is 45 to 65% by mass with respect to the total mass of the crosslinked ethylene / α-olefin copolymer (C). The ethylene / α-olefin copolymer A) is an ethylene / propylene copolymer, and the ethylene / α-olefin copolymer (A) has a content of ethylene units constituting the ethylene / α-olefin copolymer (A). The total mass is preferably 45 to 65% by mass.

The thermoplastic resin composition (I) in the third aspect of the present invention is a methacrylic acid obtained by polymerizing a graft copolymer (D) and a vinyl monomer mixture (m3) containing a methacrylic acid ester. The graft copolymer (D) has a mass average molecular weight (Mw) of 26 × 10 ⁴ to 32 × 10 ⁴ and a molecular weight distribution (Mw / Mn) of 1.9 to In the presence of the ethylene / α-olefin copolymer (A) 2.5 or a crosslinked ethylene / α-olefin copolymer (C) obtained by crosslinking the ethylene / α-olefin copolymer (A), A graft copolymer obtained by polymerizing a vinyl monomer mixture (m1) containing an aromatic vinyl compound and a vinyl cyanide compound is preferred.

The thermoplastic resin composition (I) in the third aspect of the present invention is a methacrylic acid obtained by polymerizing a graft copolymer (D) and a vinyl monomer mixture (m3) containing a methacrylic acid ester. The graft copolymer (D) has a mass average molecular weight (Mw) of 26 × 10 ⁴ to 32 × 10 ⁴ and a molecular weight distribution (Mw / Mn) of 1.9 to 2.5, a vinyl containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of a crosslinked ethylene / α-olefin copolymer (C) obtained by crosslinking the ethylene / α-olefin copolymer (A) A graft copolymer obtained by polymerizing the monomer mixture (m1), wherein the crosslinked ethylene / α-olefin copolymer (C) has a gel content of the crosslinked ethylene / α-olefin copolymer. Total of polymer (C) With respect to the amount is preferably 45 to 65 mass%.

The thermoplastic resin composition (I) in the third aspect of the present invention is a methacrylic acid obtained by polymerizing a graft copolymer (D) and a vinyl monomer mixture (m3) containing a methacrylic acid ester. The graft copolymer (D) has a mass average molecular weight (Mw) of 26 × 10 ⁴ to 32 × 10 ⁴ and a molecular weight distribution (Mw / Mn) of 1.9 to 2.5, a vinyl containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of a crosslinked ethylene / α-olefin copolymer (C) obtained by crosslinking the ethylene / α-olefin copolymer (A) A graft copolymer obtained by polymerizing the monomer mixture (m1), wherein the crosslinked ethylene / α-olefin copolymer (C) has a gel content of the crosslinked ethylene / α-olefin copolymer. Total of polymer (C) With respect to the amount, a 45 to 65 wt%, it is preferable that the ethylene-alpha-olefin copolymer (A) is an ethylene-propylene copolymer.

The thermoplastic resin composition (I) in the third aspect of the present invention is a methacrylic acid obtained by polymerizing a graft copolymer (D) and a vinyl monomer mixture (m3) containing a methacrylic acid ester. The graft copolymer (D) has a mass average molecular weight (Mw) of 26 × 10 ⁴ to 32 × 10 ⁴ and a molecular weight distribution (Mw / Mn) of 1.9 to 2.5, a vinyl containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of a crosslinked ethylene / α-olefin copolymer (C) obtained by crosslinking the ethylene / α-olefin copolymer (A) A graft copolymer obtained by polymerizing the monomer mixture (m1), wherein the crosslinked ethylene / α-olefin copolymer (C) has a gel content of the crosslinked ethylene / α-olefin copolymer. Total of polymer (C) The ethylene / α-olefin copolymer (A) is an ethylene / propylene copolymer, and the ethylene / α-olefin copolymer (A) has an ethylene content of 45 to 65% by mass. The unit content is preferably 45 to 65% by mass with respect to the total mass of the constituent units constituting the ethylene / α-olefin copolymer (A).

The thermoplastic resin composition (I) in the third aspect of the present invention is a methacrylic acid obtained by polymerizing a graft copolymer (D) and a vinyl monomer mixture (m3) containing a methacrylic ester. The graft copolymer (D) has a mass average molecular weight (Mw) of 26 × 10 ⁴ to 32 × 10 ⁴ and a molecular weight distribution (Mw / Mn) of 1.9 to 2.5, a vinyl containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of a crosslinked ethylene / α-olefin copolymer (C) obtained by crosslinking the ethylene / α-olefin copolymer (A) A graft copolymer obtained by emulsion polymerization of a monomer mixture (m1), wherein the crosslinked ethylene / α-olefin copolymer (C) has a gel content of the crosslinked ethylene / α-olefin. Copolymer (C) The ethylene / α-olefin copolymer (A) is an ethylene / propylene copolymer, and the ethylene / α-olefin copolymer (A) is 45 to 65% by mass with respect to the total mass. The ethylene unit content is preferably 45 to 65% by mass based on the total mass of the constituent units constituting the ethylene / α-olefin copolymer (A).

The thermoplastic resin composition (I) in the third aspect of the present invention is a methacrylic acid obtained by polymerizing a graft copolymer (D) and a vinyl monomer mixture (m3) containing a methacrylic acid ester. The graft copolymer (D) has a mass average molecular weight (Mw) of 26 × 10 ⁴ to 32 × 10 ⁴ and a molecular weight distribution (Mw / Mn) of 1.9 to In the presence of the ethylene / α-olefin copolymer (A) 2.5 or a crosslinked ethylene / α-olefin copolymer (C) obtained by crosslinking the ethylene / α-olefin copolymer (A), A graft copolymer obtained by polymerizing a vinyl monomer mixture (m1) containing an aromatic vinyl compound and a vinyl cyanide compound. In 100% by mass of the vinyl monomer mixture (m3), methacryl Acid ester It is preferable that the content of is from 50 to 94% by mass, the content of the maleimide compound is from 5 to 49% by mass, and the content of the aromatic vinyl compound is from 1 to 45% by mass.

The thermoplastic resin composition (I) in the third aspect of the present invention is a methacrylic acid obtained by polymerizing a graft copolymer (D) and a vinyl monomer mixture (m3) containing a methacrylic acid ester. A graft copolymer comprising an ester resin (G) and a styrene copolymer (H) obtained by polymerizing a vinyl monomer mixture (m4) containing an aromatic vinyl compound and a vinyl cyanide compound. (D) is an ethylene / α-olefin copolymer having a mass average molecular weight (Mw) of 26 × 10 ⁴ to 32 × 10 ⁴ and a molecular weight distribution (Mw / Mn) of 1.9 to 2.5 ( A) or a vinyl-based monomer containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of a crosslinked ethylene / α-olefin copolymer (C) obtained by crosslinking the ethylene / α-olefin copolymer (A). Mass A graft copolymer obtained by polymerizing the mixture (m1), wherein 100% by mass of the vinyl monomer mixture (m3) has a methacrylic acid ester content of 50 to 94% by mass, The content is 5 to 49% by mass, the content of the aromatic vinyl compound is 1 to 45% by mass, and the content of the aromatic vinyl compound is 15% in 100% by mass of the vinyl monomer mixture (m4). The content of the vinyl cyanide compound is preferably 5 to 85% by mass.

The thermoplastic resin composition (I) according to the fourth aspect of the present invention comprises an aromatic vinyl compound and cyanide in the presence of the graft copolymer (D) and the crosslinked acrylate rubber polymer (E). It is obtained by polymerizing a graft copolymer (F) obtained by polymerizing a vinyl monomer mixture (m2) containing a vinyl chloride compound and a vinyl monomer mixture (m3) containing a methacrylic acid ester. The graft copolymer (D) has a mass average molecular weight (Mw) of 26 × 10 ⁴ to 32 × 10 ⁴ and a molecular weight distribution (Mw / Mn) of 1. The presence of a 9 to 2.5 ethylene / α-olefin copolymer (A) or a crosslinked ethylene / α-olefin copolymer (C) obtained by crosslinking the ethylene / α-olefin copolymer (A) Under the aromatic vinyl A graft copolymer obtained by polymerizing a vinyl monomer mixture (m1) containing a compound and a vinyl cyanide compound is preferred.

The thermoplastic resin composition (I) according to the fourth aspect of the present invention comprises an aromatic vinyl compound and cyanide in the presence of the graft copolymer (D) and the crosslinked acrylate rubber polymer (E). It is obtained by polymerizing a graft copolymer (F) obtained by polymerizing a vinyl monomer mixture (m2) containing a vinyl chloride compound and a vinyl monomer mixture (m3) containing a methacrylic acid ester. The graft copolymer (D) has a mass average molecular weight (Mw) of 26 × 10 ⁴ to 32 × 10 ⁴ and a molecular weight distribution (Mw / Mn) of 1. Aromatic vinyl compound and vinyl cyanide compound in the presence of a crosslinked ethylene / α-olefin copolymer (C) obtained by crosslinking the ethylene / α-olefin copolymer (A), which is .9 to 2.5 Including vinyl A graft copolymer obtained by polymerizing the monomer mixture (m1), wherein the crosslinked ethylene / α-olefin copolymer (C) has a gel content of the crosslinked ethylene / α-olefin copolymer It is preferably 45 to 65% by mass with respect to the total mass of the combined (C).

The thermoplastic resin composition (I) according to the fourth aspect of the present invention comprises an aromatic vinyl compound and cyanide in the presence of the graft copolymer (D) and the crosslinked acrylate rubber polymer (E). It is obtained by polymerizing a graft copolymer (F) obtained by polymerizing a vinyl monomer mixture (m2) containing a vinyl chloride compound and a vinyl monomer mixture (m3) containing a methacrylic acid ester. The graft copolymer (D) has a mass average molecular weight (Mw) of 26 × 10 ⁴ to 32 × 10 ⁴ and a molecular weight distribution (Mw / Mn) of 1. Aromatic vinyl compound and vinyl cyanide compound in the presence of a crosslinked ethylene / α-olefin copolymer (C) obtained by crosslinking the ethylene / α-olefin copolymer (A), which is .9 to 2.5 Including vinyl A graft copolymer obtained by polymerizing the monomer mixture (m1), wherein the crosslinked ethylene / α-olefin copolymer (C) has a gel content of the crosslinked ethylene / α-olefin copolymer The ethylene / α-olefin copolymer (A) is preferably an ethylene / propylene copolymer in an amount of 45 to 65% by mass based on the total mass of the polymer (C).

The thermoplastic resin composition (I) according to the fourth aspect of the present invention comprises an aromatic vinyl compound and cyanide in the presence of the graft copolymer (D) and the crosslinked acrylate rubber polymer (E). It is obtained by polymerizing a graft copolymer (F) obtained by polymerizing a vinyl monomer mixture (m2) containing a vinyl chloride compound and a vinyl monomer mixture (m3) containing a methacrylic acid ester. The graft copolymer (D) has a mass average molecular weight (Mw) of 26 × 10 ⁴ to 32 × 10 ⁴ and a molecular weight distribution (Mw / Mn) of 1. Aromatic vinyl compound and vinyl cyanide compound in the presence of a crosslinked ethylene / α-olefin copolymer (C) obtained by crosslinking the ethylene / α-olefin copolymer (A), which is .9 to 2.5 Including vinyl A graft copolymer obtained by polymerizing the monomer mixture (m1), wherein the crosslinked ethylene / α-olefin copolymer (C) has a gel content of the crosslinked ethylene / α-olefin copolymer 45 to 65% by mass relative to the total mass of the blend (C), and the crosslinked ethylene / α-olefin copolymer (C) is an ethylene / propylene copolymer, and the crosslinked ethylene / α-olefin The ethylene unit content of the copolymer (C) is preferably 45 to 65% by mass.

The thermoplastic resin composition (I) according to the fourth aspect of the present invention comprises an aromatic vinyl compound and cyanide in the presence of the graft copolymer (D) and the crosslinked acrylate rubber polymer (E). It is obtained by polymerizing a graft copolymer (F) obtained by polymerizing a vinyl monomer mixture (m2) containing a vinyl chloride compound and a vinyl monomer mixture (m3) containing a methacrylic acid ester. The graft copolymer (D) has a mass average molecular weight (Mw) of 26 × 10 ⁴ to 32 × 10 ⁴ and a molecular weight distribution (Mw / Mn) of 1. Aromatic vinyl compound and vinyl cyanide compound in the presence of a crosslinked ethylene / α-olefin copolymer (C) obtained by crosslinking the ethylene / α-olefin copolymer (A), which is .9 to 2.5 Including vinyl A graft copolymer obtained by emulsion polymerization of the monomer mixture (m1), wherein the crosslinked ethylene / α-olefin copolymer (C) has a gel content of the crosslinked ethylene / α-olefin copolymer. 45 to 65% by mass based on the total mass of the polymer (C), and the ethylene / α-olefin copolymer (A) is an ethylene / propylene copolymer, The ethylene unit content of the polymer (A) is preferably 45 to 65% by mass based on the total mass of the constituent units constituting the ethylene / α-olefin copolymer (A).

The thermoplastic resin composition (I) according to the fourth aspect of the present invention comprises an aromatic vinyl compound and cyanide in the presence of the graft copolymer (D) and the crosslinked acrylate rubber polymer (E). It is obtained by polymerizing a graft copolymer (F) obtained by polymerizing a vinyl monomer mixture (m2) containing a vinyl chloride compound and a vinyl monomer mixture (m3) containing a methacrylic acid ester. The graft copolymer (D) has a mass average molecular weight (Mw) of 26 × 10 ⁴ to 32 × 10 ⁴ and a molecular weight distribution (Mw / Mn) of 1. The presence of a 9 to 2.5 ethylene / α-olefin copolymer (A) or a crosslinked ethylene / α-olefin copolymer (C) obtained by crosslinking the ethylene / α-olefin copolymer (A) Under the aromatic vinyl A graft copolymer obtained by polymerizing a vinyl monomer mixture (m1) containing a compound and a vinyl cyanide compound, wherein 100% by mass of the vinyl monomer mixture (m2) is an aromatic vinyl compound Is preferably 65 to 82% by mass, and the vinyl cyanide compound content is preferably 18 to 35% by mass.

The thermoplastic resin composition (I) according to the fourth aspect of the present invention comprises an aromatic vinyl compound and cyanide in the presence of the graft copolymer (D) and the crosslinked acrylate rubber polymer (E). It is obtained by polymerizing a graft copolymer (F) obtained by polymerizing a vinyl monomer mixture (m2) containing a vinyl chloride compound and a vinyl monomer mixture (m3) containing a methacrylic acid ester. The graft copolymer (D) has a mass average molecular weight (Mw) of 26 × 10 ⁴ to 32 × 10 ⁴ and a molecular weight distribution (Mw / Mn) of 1. The presence of a 9 to 2.5 ethylene / α-olefin copolymer (A) or a crosslinked ethylene / α-olefin copolymer (C) obtained by crosslinking the ethylene / α-olefin copolymer (A) Under the aromatic vinyl A graft copolymer obtained by polymerizing a vinyl monomer mixture (m1) containing a compound and a vinyl cyanide compound, wherein 100% by mass of the vinyl monomer mixture (m2) is an aromatic vinyl compound Is 65 to 82% by mass, the vinyl cyanide compound content is 18 to 35% by mass, and 100% by mass of the vinyl monomer mixture (m3) has a methacrylic acid ester content. It is preferable that the content of the maleimide compound is 50 to 94% by mass, the content of the maleimide compound is 5 to 49% by mass, and the content of the aromatic vinyl compound is 1 to 45% by mass.

The thermoplastic resin composition (I) according to the fourth aspect of the present invention comprises an aromatic vinyl compound and cyanide in the presence of the graft copolymer (D) and the crosslinked acrylate rubber polymer (E). It is obtained by polymerizing a graft copolymer (F) obtained by polymerizing a vinyl monomer mixture (m2) containing a vinyl chloride compound and a vinyl monomer mixture (m3) containing a methacrylic acid ester. A methacrylic acid ester resin (G) and a styrene copolymer (H) obtained by polymerizing a vinyl monomer mixture (m4) containing an aromatic vinyl compound and a vinyl cyanide compound, the graft The copolymer (D) is an ethylene / α-olefin copolymer having a mass average molecular weight (Mw) of 26 × 10 ⁴ to 32 × 10 ⁴ and a molecular weight distribution (Mw / Mn) of 1.9 to 2.5. Polymer (A) Is a vinyl monomer containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of the crosslinked ethylene / α-olefin copolymer (C) obtained by crosslinking the ethylene / α-olefin copolymer (A). A graft copolymer obtained by polymerizing the mixture (m1), wherein 100% by mass of the vinyl monomer mixture (m2) has an aromatic vinyl compound content of 65 to 82% by mass, cyanide The content of the vinyl chloride compound is 18 to 35% by mass, the content of the methacrylic acid ester is 50 to 94% by mass, and the content of the maleimide compound is 100% by mass of the vinyl monomer mixture (m3). The content of the aromatic vinyl compound is 5 to 49% by mass, the content of the aromatic vinyl compound is 1 to 45% by mass, and the content of the aromatic vinyl compound is 15 to 95% in 100% by mass of the vinyl monomer mixture (m4). An amount%, a content of the vinyl cyanide compound is preferably 5 to 85 mass%.

The thermoplastic resin composition (I) according to the fifth aspect of the present invention includes a graft copolymer (D), a polyorganosiloxane (La), a unit derived from a (meth) acrylic acid ester, and a crosslinking agent. In the presence of a composite rubber-like polymer (L1) comprising a poly (meth) acrylate (Lb) having either one or both of a unit derived from or a unit derived from a graft crossing agent, an aromatic vinyl compound and Obtained by polymerizing a graft copolymer (M) obtained by polymerizing a vinyl monomer mixture (m5) containing a vinyl cyanide compound and a vinyl monomer mixture (m3) containing a methacrylic acid ester. The graft copolymer (D) has a mass average molecular weight (Mw) of 26 × 10 ⁴ to 32 × 10 ⁴ and a molecular weight distribution ( Mw / Mn) 1.9 to 2.5 ethylene / α-olefin copolymer (A) or cross-linked ethylene / α-olefin copolymer obtained by crosslinking the ethylene / α-olefin copolymer (A) A graft copolymer obtained by polymerizing a vinyl monomer mixture (m1) containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of the compound (C) is preferable.

The thermoplastic resin composition (I) according to the fifth aspect of the present invention includes a graft copolymer (D), a polyorganosiloxane (La), a unit derived from a (meth) acrylic acid ester, and a crosslinking agent. In the presence of a composite rubber-like polymer (L1) comprising a poly (meth) acrylate (Lb) having either one or both of a unit derived from or a unit derived from a graft crossing agent, an aromatic vinyl compound and Obtained by polymerizing a graft copolymer (M) obtained by polymerizing a vinyl monomer mixture (m5) containing a vinyl cyanide compound and a vinyl monomer mixture (m3) containing a methacrylic acid ester. The graft copolymer (D) has a mass average molecular weight (Mw) of 26 × 10 ⁴ to 32 × 10 ⁴ and a molecular weight distribution ( In the presence of the crosslinked ethylene / α-olefin copolymer (C) obtained by crosslinking the ethylene / α-olefin copolymer (A) having an Mw / Mn) of 1.9 to 2.5, aromatic vinyl is used. A graft copolymer obtained by polymerizing a vinyl monomer mixture (m1) containing a compound and a vinyl cyanide compound, wherein the gel content of the crosslinked ethylene / α-olefin copolymer (C) is The amount of the crosslinked ethylene / α-olefin copolymer (C) is preferably 45 to 65% by mass based on the total mass.

The thermoplastic resin composition (I) according to the fifth aspect of the present invention includes a graft copolymer (D), a polyorganosiloxane (La), a unit derived from a (meth) acrylic acid ester, and a crosslinking agent. In the presence of a composite rubber-like polymer (L1) comprising a poly (meth) acrylate (Lb) having either one or both of a unit derived from or a unit derived from a graft crossing agent, an aromatic vinyl compound and Obtained by polymerizing a graft copolymer (M) obtained by polymerizing a vinyl monomer mixture (m5) containing a vinyl cyanide compound and a vinyl monomer mixture (m5) containing a methacrylic acid ester. The graft copolymer (D) has a mass average molecular weight (Mw) of 26 × 10 ⁴ to 32 × 10 ⁴ and a molecular weight distribution ( In the presence of the crosslinked ethylene / α-olefin copolymer (C) obtained by crosslinking the ethylene / α-olefin copolymer (A) having an Mw / Mn) of 1.9 to 2.5, aromatic vinyl is used. A graft copolymer obtained by polymerizing a vinyl monomer mixture (m1) containing a compound and a vinyl cyanide compound, wherein the gel content of the crosslinked ethylene / α-olefin copolymer (C) is 45 to 65% by mass with respect to the total mass of the crosslinked ethylene / α-olefin copolymer (C), and the ethylene / α-olefin copolymer (A) is an ethylene / propylene copolymer. It is preferable.

The thermoplastic resin composition (I) according to the fifth aspect of the present invention includes a graft copolymer (D), a polyorganosiloxane (La), a unit derived from a (meth) acrylic acid ester, and a crosslinking agent. In the presence of a composite rubber-like polymer (L1) comprising a poly (meth) acrylate (Lb) having either one or both of a unit derived from or a unit derived from a graft crossing agent, an aromatic vinyl compound and Obtained by polymerizing a graft copolymer (M) obtained by polymerizing a vinyl monomer mixture (m5) containing a vinyl cyanide compound and a vinyl monomer mixture (m3) containing a methacrylic acid ester. The graft copolymer (D) has a mass average molecular weight (Mw) of 26 × 10 ⁴ to 32 × 10 ⁴ and a molecular weight distribution ( In the presence of the crosslinked ethylene / α-olefin copolymer (C) obtained by crosslinking the ethylene / α-olefin copolymer (A) having an Mw / Mn) of 1.9 to 2.5, aromatic vinyl is used. A graft copolymer obtained by polymerizing a vinyl monomer mixture (m1) containing a compound and a vinyl cyanide compound, wherein the gel content of the crosslinked ethylene / α-olefin copolymer (C) is 45 to 65% by mass with respect to the total mass of the crosslinked ethylene / α-olefin copolymer (C), and the ethylene unit content of the ethylene / α-olefin copolymer (A) is The content is preferably 45 to 65% by mass with respect to the total mass of the constituent units constituting the ethylene / α-olefin copolymer (A).

The thermoplastic resin composition (I) according to the fifth aspect of the present invention includes a graft copolymer (D), a polyorganosiloxane (La), a unit derived from a (meth) acrylic acid ester, and a crosslinking agent. In the presence of a composite rubber-like polymer (L1) comprising a poly (meth) acrylate (Lb) having either one or both of a unit derived from or a unit derived from a graft crossing agent, an aromatic vinyl compound and Obtained by polymerizing a graft copolymer (M) obtained by polymerizing a vinyl monomer mixture (m5) containing a vinyl cyanide compound and a vinyl monomer mixture (m3) containing a methacrylic acid ester. The graft copolymer (D) has a mass average molecular weight (Mw) of 26 × 10 ⁴ to 32 × 10 ⁴ and a molecular weight distribution ( Aromatic vinyl in the presence of a crosslinked ethylene / α-olefin copolymer (C) obtained by crosslinking the ethylene / α-olefin copolymer (A) having a Mw / Mn) of 1.9 to 2.5 A graft copolymer obtained by emulsion polymerization of a vinyl monomer mixture (m1) containing a compound and a vinyl cyanide compound, the gel content of the crosslinked ethylene / α-olefin copolymer (C) Is 45 to 65% by mass with respect to the total mass of the crosslinked ethylene / α-olefin copolymer (C), and the ethylene unit content of the ethylene / α-olefin copolymer (A) is: The content is preferably 45 to 65% by mass based on the total mass of the constituent units constituting the ethylene / α-olefin copolymer (A).

The thermoplastic resin composition (I) according to the fifth aspect of the present invention includes a graft copolymer (D), a polyorganosiloxane (La), a unit derived from a (meth) acrylic acid ester, and a crosslinking agent. In the presence of a composite rubber-like polymer (L1) comprising a poly (meth) acrylate (Lb) having either one or both of a unit derived from or a unit derived from a graft crossing agent, an aromatic vinyl compound and Obtained by polymerizing a graft copolymer (M) obtained by polymerizing a vinyl monomer mixture (m5) containing a vinyl cyanide compound and a vinyl monomer mixture (m3) containing a methacrylic acid ester. The graft copolymer (D) has a mass average molecular weight (Mw) of 26 × 10 ⁴ to 32 × 10 ⁴ and a molecular weight distribution ( Methyleneethylene / α-olefin copolymer (A) having a Mw / Mn) of 1.9 to 2.5 or a crosslinked ethylene / α-olefin copolymer obtained by crosslinking the ethylene / α-olefin copolymer (A). A graft copolymer obtained by polymerizing a vinyl monomer mixture (m1) containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of the compound (C), wherein the composite rubber-like polymer ( The volume average particle diameter of L1) is preferably 0.05 to 0.18 μm.

The thermoplastic resin composition (I) according to the fifth aspect of the present invention includes a graft copolymer (D), a polyorganosiloxane (La), a unit derived from a (meth) acrylic acid ester, and a crosslinking agent. In the presence of a composite rubber-like polymer (L1) comprising a poly (meth) acrylate (Lb) having either one or both of a unit derived from or a unit derived from a graft crossing agent, an aromatic vinyl compound and Obtained by polymerizing a graft copolymer (M) obtained by polymerizing a vinyl monomer mixture (m5) containing a vinyl cyanide compound and a vinyl monomer mixture (m3) containing a methacrylic acid ester. The graft copolymer (D) has a mass average molecular weight (Mw) of 26 × 10 ⁴ to 32 × 10 ⁴ and a molecular weight distribution ( Methyleneethylene / α-olefin copolymer (A) having a Mw / Mn) of 1.9 to 2.5 or a crosslinked ethylene / α-olefin copolymer obtained by crosslinking the ethylene / α-olefin copolymer (A). A graft copolymer obtained by polymerizing a vinyl monomer mixture (m1) containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of the compound (C), wherein the composite rubber-like polymer ( L1) has a volume average particle diameter of 0.05 to 0.18 μm, and in 100% by mass of the vinyl monomer mixture (m3), the content of methacrylic acid ester is 50 to 94% by mass. Is preferably 5 to 49% by mass, and the aromatic vinyl compound content is preferably 1 to 45% by mass.

The thermoplastic resin composition (I) according to the fifth aspect of the present invention includes a graft copolymer (D), a polyorganosiloxane (La), a unit derived from a (meth) acrylic acid ester, and a crosslinking agent. In the presence of a composite rubber-like polymer (L1) comprising a poly (meth) acrylate (Lb) having either one or both of a unit derived from or a unit derived from a graft crossing agent, an aromatic vinyl compound and Obtained by polymerizing a graft copolymer (M) obtained by polymerizing a vinyl monomer mixture (m5) containing a vinyl cyanide compound and a vinyl monomer mixture (m3) containing a methacrylic acid ester. Obtained by polymerizing the resulting methacrylic ester resin (G) with a vinyl monomer mixture (m4) containing an aromatic vinyl compound and a vinyl cyanide compound And a polymer (H), the graft copolymer (D) is the weight average molecular weight (Mw) was ^{26 × 10 4 ~ 32 × 10} 4, a molecular weight distribution (Mw / Mn) of 1.9 to In the presence of an ethylene / α-olefin copolymer (A) 2.5 or a crosslinked ethylene / α-olefin copolymer (C) obtained by crosslinking the ethylene / α-olefin copolymer (A), A graft copolymer obtained by polymerizing a vinyl monomer mixture (m1) containing an aromatic vinyl compound and a vinyl cyanide compound, and the volume average particle diameter of the composite rubber-like polymer (L1) is: 0.05 to 0.18 μm, in 100% by mass of the vinyl monomer mixture (m3), the content of methacrylic acid ester is 50 to 94% by mass, and the content of maleimide compound is 5 to 49% by mass. , Aromatic vinyl compounds The content is 1 to 45% by mass, and the content of the aromatic vinyl compound is 15 to 95% by mass in 100% by mass of the vinyl monomer mixture (m4). The rate is preferably 5 to 85% by mass.

Hereinafter, an example is shown concretely. However, the present invention is not limited to these examples.
In the following, “%” means “mass%” and “part” means “part by mass”.
Various measurements and evaluation methods in the following examples and comparative examples are as follows.

"Measuring method"
<Measurement Method of Mass Average Molecular Weight (Mw), Molecular Weight Distribution (Mw / Mn)>
For the ethylene / α-olefin copolymer, GPC (GPC: “GPC / V2000” manufactured by Waters Inc., column: “Shodex AT-G + AT-806MS” manufactured by Showa Denko KK) was used and o-dichlorobenzene (145 ° C.). ) Was used as a solvent, and the weight average molecular weight (Mw) and number average molecular weight molecular weight (Mn) in terms of polystyrene were measured to calculate the molecular weight distribution (Mw / Mn).

<Method for measuring acid value>
Measured according to JISK2501.

<Measurement method 1 of volume average particle diameter>
The volume average particle diameter (MV) of the aqueous olefin resin dispersion (C) was measured using Microtrac (manufactured by Nikkiso Co., Ltd., “Nanotrack 150”) using pure water as a measurement solvent.

<Measurement method of gel content>
0.5 g of a coagulated powder sample [D1] obtained by coagulating an aqueous or solvent dispersion of a crosslinked ethylene / α-olefin copolymer (C) with dilute sulfuric acid, washing with water and drying in 200 mL of toluene at 110 ° C. And then filtered through a 200 mesh wire mesh, the residue is dried, the mass of the dried product [D2] is measured, and the crosslinked ethylene / α-olefin copolymer ( The gel content of C) was determined.
Gel content rate (mass%) = dry substance amount [D2] (g) / coagulated powder sample mass [D1] (g) × 100 (1)

<Measurement method of graft ratio>
1 g of the graft copolymer (D) is added to 80 mL of acetone and heated to reflux at 65 to 70 ° C. for 3 hours. The mixture was centrifuged at 14,000 rpm for 30 minutes to separate a precipitation component (acetone insoluble component) and an acetone solution (acetone soluble component). And the precipitation component (acetone insoluble component) was dried, the mass (Y (g)) was measured, and the graft ratio was computed by following formula (2). In Formula (2), Y is the mass (g) of the acetone-insoluble component of the graft copolymer (D), X is the total mass (g) of the graft copolymer (D) used to determine Y, The rubber fraction is the content ratio of the graft copolymer (D) in terms of solid content of the ethylene / α-olefin copolymer (A) or the crosslinked ethylene / α-olefin copolymer (C).
Graft ratio (mass%) = {(Y−X × rubber fraction) / X × rubber fraction} × 100 (2)

"Evaluation methods"
<Melt-kneading 1>
To 100 parts of the total amount of the graft copolymer (D) and the hard component (J), 0.5 part of carbon black is added and mixed. PCM30 ") was melt kneaded at a cylinder temperature of 200 to 260 ° C and a vacuum of 93.325 kPa to obtain a thermoplastic resin composition (1). Moreover, after melt-kneading as needed, pelletization was performed using a pelletizer (“SH type pelletizer” manufactured by Souken Co., Ltd.).

<Melting and kneading 2>
To 100 parts of the total amount of the graft copolymer (D) and the hard component (J), 0.8 parts of carbon black is added and mixed, and a twin screw extruder with a 30 mmφ vacuum vent (Ikegai, “ PCM30 ”) was melt kneaded at a cylinder temperature of 200 to 260 ° C. and a vacuum of 93.325 kPa to obtain a thermoplastic resin composition (2). About the obtained thermoplastic resin composition (2), pelletization was performed using the pelletizer ("SH type pelletizer" by Soken Co., Ltd.).

(Measurement of melt volume rate (MVR))
The thermoplastic resin composition (1) was measured in accordance with ISO 1133 standard. In addition, MVR becomes a standard of the fluidity | liquidity of a thermoplastic resin composition.

<Injection molding 1>
The pellets of the thermoplastic resin composition (1) obtained by melt-kneading are subjected to conditions of cylinder temperature 200 to 260 ° C. and mold temperature 60 ° C. using an injection molding machine (“TOSHIKI MACHINE Co., Ltd.,“ IS55FP-1.5A ”). Then, a molded product having a length of 80 mm, a width of 10 cm, and a thickness of 4 mm was molded and used as a molded product for measuring flexural modulus and a molded product for Charpy impact test (molded product (Ma1)).

<Injection molding 2>
The pellets of the thermoplastic resin composition (2) obtained by melt-kneading are subjected to conditions of cylinder temperature 200 to 260 ° C. and mold temperature 60 ° C. using an injection molding machine (“TOSHIKI MACHINE Co., Ltd.,“ IS55FP-1.5A ”). Then, a black colored flat plate (molded product (Ma2)) having a length of 10 cm, a width of 10 cm, and a thickness of 2 mm was formed. The molded product (Ma2) was used as a molded product for evaluating glossiness, a molded product for evaluating color development, and a molded product for evaluating scratch resistance.

(Measurement of flexural modulus)
With respect to the molded article (Ma1) (test piece), the flexural modulus was measured in accordance with ISO 178 standard.

(Evaluation of impact resistance: Charpy impact test)
The molded product (Ma1) was subjected to a Charpy impact test (notched) at 23 ° C. in accordance with ISO 179, and the Charpy impact strength was measured.

(Glossiness evaluation 1)
The reflectance of the molded product (Ma2) was measured with a digital variable gloss meter (“UGV-5D” manufactured by Suga Test Instruments Co., Ltd.) under conditions of an incident angle of 60 ° and a reflection angle of 60 °. Higher reflectance means better gloss.

(Evaluation of color development 1)
For the molded product (Ma2), a spectral colorimeter (manufactured by Konica Minolta Optics, “CM-3500d”) is used, and the lightness L ^{* is set} to SCE (correct) using a d / 8 (diffuse illumination / 8-degree light receiving system) optical system. It was measured by the reflected light removal method. The L ^* measured in this way is referred to as “L ^* (ma)”. A lower L ^* means better color developability.

(Scratch resistance evaluation 1)
As shown in FIG. 1, a rod-like jig 10 having a tip portion 11 formed in a substantially hemispherical shape was prepared, and the tip portion 11 was covered with a laminated sheet 12 in which eight sheets of gauze were stacked. The tip portion 11 covered with the laminated sheet 12 is brought into contact with the surface of the molded product (Ma2) 13 so that the rod-shaped jig 10 is at a right angle, and the tip portion 11 is brought into contact with the surface of the molded product (Ma2) 13. Was slid in the horizontal direction (arrow direction in the figure) and reciprocated 100 times to scratch the surface of the molded product (Ma2) 13. At that time, the applied load was 1 kg. The molded product (Ma2) 13 having a scratched surface is referred to as “molded product (Mc2)”.
The lightness L ^* of the surface of the molded product (Mc2) was measured by the SCE method using a spectrocolorimeter. The L ^* measured in this way is referred to as “L ^* (mc)”.

Judgment of scratch resistance 1:
A determination index ΔL ^* of the degree of conspicuousness of scratches on the molded product (Mc2) was calculated from the following formula (3).
As the absolute value of ΔL ^* is larger, the scratches are more conspicuous.
ΔL ^* = L ^* (mc) −L ^* (ma) (3)
When the absolute value of ΔL ^* is 3.0 or less, scratches are not noticeable and the design of the molded product is not impaired.
When the absolute value of ΔL ^* is more than 3.0 to 7.0 or less, scratches are not noticeable and the design properties of the molded product are not impaired.
When the absolute value of ΔL ^* is more than 7.0, scratches are conspicuous and the design of the molded product is impaired.

Determination of scratch resistance 2:
10-point average roughness (Rz jis) of the molded product (Mc2) using a shape measurement laser microscope (manufactured by Keyence Corporation, “VK-9700”) as an index for determining the ease of scratching of the molded product (Ma2) Was measured. The larger the value of Rz jis, the easier it is to scratch.

"Various ingredients"
In the following examples, the following component (A), olefin resin aqueous dispersion (B), crosslinked ethylene / α-olefin copolymer (C), graft copolymer (D), and hard component (J) were used. .

<(A) component: ethylene / α-olefin copolymer (A) or an alternative thereof> (Preparation of ethylene / propylene copolymer (A-1A))
After sufficiently substituting the stainless polymerization tank equipped with a 20 L stirrer with nitrogen, 10 L of dehydrated and purified hexane was added, and ethyl aluminum sesquichloride (Al (C ₂ H ₅ ) _1.5 · Cl prepared to 8.0 mmol / L was obtained _{. 5} ) A hexane solution of 5 L / h was continuously supplied for 1 hour, and then a hexane solution of VO (OC ₂ H ₅ ) Cl ₂ adjusted to 0.8 mmol / L as a catalyst was further added at 5 L / h. By volume, hexane was continuously fed in an amount of 5 L / h. On the other hand, the polymerization solution was continuously extracted from the upper part of the polymerization tank so that the polymerization solution in the polymerization vessel was always 10 L. Next, ethylene was supplied in an amount of 2000 L / h, propylene in an amount of 1000 L / h, and hydrogen in an amount of 8 L / h using a bubbling tube, and a polymerization reaction was performed at 35 ° C.
A polymerization reaction was performed under the above conditions to obtain a polymerization solution containing an ethylene / propylene copolymer (A-1A). The obtained polymerization solution was deashed with hydrochloric acid, poured into methanol for precipitation, and then dried to obtain an ethylene / propylene copolymer (A-1A). Table 1A shows the properties of the ethylene / propylene copolymer (A-1A).

(Preparation of ethylene / propylene copolymers (A-2A) to (A-8A))
The ethylene / propylene copolymers (A-2A) to (A-8A) were prepared in the same manner as the ethylene / propylene copolymer (A-1A) except that the hydrogen supply amount was changed as shown in Table 1A. Obtained. Table 1A shows the polymer properties of the ethylene / propylene copolymers (A-2A) to (A-8A).

(Preparation of ethylene / propylene copolymer (A-9A))
After sufficiently substituting the stainless polymerization tank equipped with a 20 L stirrer with nitrogen, 10 L of dehydrated and purified hexane was added, and 110 NL of propylene and 800 mL of hydrogen were added. After heating to 40 ° C., it was pressurized with ethylene so that the total pressure was 0.6 MPa [gage]. When the internal pressure of the autoclave reached 0.6 MPa [gage], 10 mL of a 1.0 mM / mL hexane solution of triisobutylaluminum (TIBA) was injected with nitrogen. Subsequently, triphenylcarbenium (tetrakispentafluorophenyl) borate prepared in advance was converted to boron in an amount of 0.16 mM, [dimethyl (t-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) silane] Polymerization was initiated by injecting 30 mL of a toluene solution containing titanium chloride in an amount of 0.0004 mM with nitrogen. Thereafter, the temperature was adjusted to 40 ° C. for 5 minutes, and ethylene was supplied so that the pressure became 0.6 MPa [gage]. Five minutes after the start of the polymerization, 50 mL of methanol was inserted to terminate the polymerization, and the pressure was released to atmospheric pressure to obtain a polymerization solution containing an ethylene / propylene copolymer (A-9A). The obtained polymerization solution was deashed with hydrochloric acid, poured into methanol for precipitation, and then dried to obtain an ethylene / propylene copolymer (A-9A). Table 3A shows the polymer properties of the ethylene / propylene copolymer (A-9A).

(Preparation of ethylene / propylene copolymer (A-10A))
Mix 20 parts of ethylene / propylene copolymer (A-1A) and 80 parts of ethylene / propylene copolymer (A-9A), and use a twin screw extruder with a 30 mmφ vacuum vent ("PCM30" manufactured by Ikegai Co., Ltd.) The mixture was melt kneaded at 200 ° C. and 93.325 kPa vacuum to prepare an ethylene / propylene copolymer (A-10A). Table 3A shows the polymer properties of the ethylene / propylene copolymer (A-10A).

(Preparation of ethylene / propylene copolymer (A-11A))
The ethylene / propylene copolymer (A-11A) was prepared in the same manner as the ethylene / propylene copolymer (A-1A) except that VCl ₄ was used instead of VO (OC ₂ H ₅ ) Cl ₂ as a catalyst. Obtained. Table 1A shows the properties of the ethylene / propylene copolymer (A-11A).

(Preparation of ethylene / propylene copolymer (A-12A))
Mix 75 parts of ethylene / propylene copolymer (A-1A) and 25 parts of ethylene / propylene copolymer (A-11A), and use a twin screw extruder with a 30 mmφ vacuum vent ("PCM30" manufactured by Ikegai Co., Ltd.) The mixture was melt-kneaded at 200 ° C. and 93.325 kPa vacuum to prepare an ethylene / propylene copolymer (A-12A). Table 3A shows the properties of the ethylene / propylene copolymer (A-12A) polymer.

(Preparation of ethylene / propylene copolymer (A-13A))
Mix 50 parts of ethylene / propylene copolymer (A-1A) and 50 parts of ethylene / propylene copolymer (A-11A), and use a twin screw extruder with a 30 mmφ vacuum vent ("PCM30" manufactured by Ikegai Co., Ltd.) The mixture was melt-kneaded at 200 ° C. and 93.325 kPa vacuum to prepare an ethylene / propylene copolymer (A-13A). Table 3A shows the properties of the ethylene / propylene copolymer (A-13A).

(Preparation of ethylene / propylene copolymer (A-14A))
Mix 20 parts of ethylene / propylene copolymer (A-1A) and 80 parts of ethylene / propylene copolymer (A-11A), and use a twin screw extruder with a 30 mmφ vacuum vent (Ikegai Co., Ltd., “PCM30”). The mixture was melt-kneaded at 200 ° C. and 93.325 kPa vacuum to prepare an ethylene / propylene copolymer (A-14A). Table 3A shows the properties of the ethylene / propylene copolymer (A-14A).

(Preparation of ethylene / propylene / non-conjugated diene copolymer (A-15A) and ethylene / 1-butene copolymer (A-16A))
As shown in Table 2A, an ethylene / propylene / non-conjugated diene copolymer was prepared in the same manner as the ethylene / propylene copolymer (A-1A) except that the supply amounts of ethylene, propylene, 1-butene and hydrogen were changed. (A-15A), an ethylene / 1-butene copolymer (A-16A) was obtained. The properties of the obtained polymer are shown in Table 2A.

(Preparation of ethylene / 1-octene copolymer (A-17A))
0.5 mg of bis (1,3-dimethylcyclopentadienyl) zirconium dichloride is placed in a glass flask thoroughly substituted with nitrogen, and 1.57 mL of a toluene solution of methylaminoxan (Al; 1.1 mol / L), A catalyst solution was obtained by adding 2.76 mL of toluene.
6000 mL of hexane and 4000 mL of 1-octene were inserted into a 20 L autoclave equipped with a stirrer sufficiently purged with nitrogen, and the temperature inside the system was raised to 70 ° C. Subsequently, polymerization was initiated by injecting 1 mmol of triisobutylaluminum and 5 mL of the catalyst solution prepared above with ethylene. Thereafter, by continuously supplying only ethylene, the total pressure was kept at 0.39 MPa [gage], and polymerization was carried out at 80 ° C. for 1 hour.
A polymerization reaction was performed under the above conditions to obtain a polymerization solution containing an ethylene / 1-octene copolymer.
The obtained polymerization solution was deashed with hydrochloric acid, poured into methanol for precipitation, and then dried to obtain an ethylene / 1-octene copolymer (A-17A). The properties of the obtained polymer are shown in Table 3A.

(Preparation of ethylene / propylene copolymers (A-18A) to (A-23A))
As shown in Table 2A, ethylene / propylene copolymers (A-18A) to (A-18A) to (A) are the same as ethylene / propylene copolymers (A-1A) except that the supply amounts of ethylene, propylene, and hydrogen are changed. -23A) was obtained. The properties of the obtained polymer are shown in Table 2A.

<Olefin resin aqueous dispersion (B)> (Preparation of aqueous olefin resin dispersion (B-1A))
100 parts of ethylene / propylene copolymer (A-1A) and maleic anhydride-modified polyethylene (Mitsui Chemicals, "Mitsui High Wax 2203A", as the acid-modified olefin polymer (K), mass average molecular weight: 2,700, Acid value: 30 mg / g) 15 parts of (K-1A) and 3 parts of potassium oleate as an anionic emulsifier were mixed.
Next, this mixture was supplied at a rate of 4 kg / hour from the hopper of a twin screw extruder (“Ikegai Co., Ltd.,“ PCM-30 ”L / D = 40) at a continuous rate of 240 g / hour. The mixture was heated to 220 ° C. and melt kneaded, and the resulting melt kneaded product was extruded.
Subsequently, the melt-kneaded product was continuously supplied to a cooling device attached to the tip of the extruder and cooled to 90 ° C. The taken-out solid was poured into warm water at 80 ° C. and continuously dispersed to obtain an aqueous olefin resin dispersion (B-1A) having a volume average particle size of 0.38 μm.

(Preparation of aqueous olefin resin dispersions (B-2A) to (B-23A))
As shown in Tables 4A to 6A, the same procedure as in the aqueous olefin resin dispersion (C-1A) was conducted except that (A-1A) was changed to (A-2A) to (A-23A) as the component (A). Thus, aqueous olefin resin dispersions (B-2A) to (B-23A) were obtained. The volume average particle diameters of the respective olefin resin aqueous dispersions (B-2A) to (B-23A) are shown in Tables 4A to 6A.

<Crosslinked ethylene / α-olefin copolymer (C)> (Preparation of crosslinked olefin resin (C-1A))
To 100 parts of the solid content of the crosslinked olefin resin aqueous dispersion (B-1A), 0.5 part of t-butylcumyl peroxide as an organic peroxide and 1 part of divinylbenzene as a polyfunctional compound are added, By reacting at 130 ° C. for 5 hours, an aqueous dispersion of a crosslinked ethylene / α-olefin copolymer (C-1A) was prepared. The gel content of the crosslinked ethylene / α-olefin copolymer (C-1A) was measured and found to be 51%.

(Preparation of crosslinked ethylene / α-olefin copolymers (C-2A) to (C-23A))
As shown in Tables 7A to 9A, the same as the cross-linked ethylene / α-olefin copolymer (C-1A) except that the type of the aqueous olefin resin dispersion (B) and the number of added parts of t-butylcumyl peroxide were changed. Thus, an aqueous dispersion of the crosslinked ethylene / α-olefin copolymers (C-2A) to (C-23A) was obtained. Tables 7A to 9A show the results of measuring the gel contents of the respective crosslinked olefin resins (C-2A) to (C-23A).

(Preparation of crosslinked ethylene / α-olefin copolymers (C-24A) to (C-31A))
As shown in Table 10A, the crosslinked ethylene / α-olefin copolymer (C-24A) to ( An aqueous dispersion of C-31A) was obtained. The results of measuring the gel content of each of the crosslinked ethylene / α-olefin copolymers (C-24A) to (C-31A) are shown in Table 10A.

<Graft Copolymer (D)> (Preparation of Graft Copolymer (D-1A))
In a stainless polymerization tank equipped with a stirrer, 180 parts of ion-exchanged water, 60 parts of an aqueous dispersion of a crosslinked ethylene / α-olefin copolymer (C-1A) in terms of solid content, 0.006 parts of ferrous sulfate, pyrophosphoric acid 0.3 parts of sodium and 0.35 parts of dextrose were charged and the temperature was set to 80 ° C. Next, 13.7 parts of acrylonitrile, 26.3 parts of styrene and 0.6 part of cumene hydroperoxide were continuously added for 150 minutes, and emulsion polymerization was carried out while keeping the polymerization temperature constant at 80 ° C. After polymerization, an antioxidant is added to the aqueous dispersion containing the obtained graft copolymer (D-1A), solids are precipitated with sulfuric acid, and after washing, dehydration and drying steps, A graft copolymer (D-1A) was obtained. The graft ratio of the graft copolymer (D-1A) was measured and found to be 40%.

(Preparation of graft copolymers (F-2A) to (F-31A))
As shown in Tables 11A to 14A, a graft copolymer (D-2A) was prepared in the same manner as the graft copolymer (D-1A) except that the type of the crosslinked ethylene / α-olefin copolymer (C) was changed. ) To (D-31A) were obtained. Tables 11A to 14A show the measurement results of the graft ratios of the respective graft copolymers (D-2) to (D-31).

(Preparation of graft copolymer (D-32A))
A stainless steel polymerization tank equipped with a stirrer was charged with 52 parts of ethylene / propylene copolymer (A-1A), 8 parts of maleic anhydride-modified polyethylene (K-1A), 300 parts of toluene, and 1 part of divinylbenzene, and the contents were 75 ° C. And stirred for 1 hour to dissolve uniformly. After sufficiently substituting with nitrogen, 0.5 part of t-butylcumyl peroxide was added, the internal temperature was raised to 130 ° C., and the reaction was performed for 5 hours. A solvent dispersion of α-olefin copolymer (C-32A) was prepared.
Thereafter, the internal temperature was lowered to 70 ° C., and 26.3 parts of styrene, 13.7 parts of acrylonitrile, 0.24 parts of tert-dodecyl mercaptan, and 0.22 parts of tert-butylperoxyisopropyl monocarbonate were added. Was heated to 110 ° C. and reacted for 4 hours, and then the internal temperature was raised to 120 ° C. and reacted for 2 hours. After polymerization, the internal temperature is cooled to 100 ° C., 0.2 part of octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenol) -propionate is added, and the reaction mixture is taken out and steam distilled. Then, unreacted substances and solvent were distilled off, and the volatile matter was substantially devolatilized at 220 ° C. and 93.325 kPa vacuum using a 30 mmφ twin-screw extruder equipped with a vacuum vent (manufactured by Ikegai Co., Ltd., “PCM30”). And pelletized to obtain a graft copolymer (D-32A). The graft ratio of the graft copolymer (D-32A) was measured and found to be 35%.

<Hard component (J)> (Preparation of styrene copolymer (H-1A))
In a stainless steel polymerization reactor equipped with a stirrer purged with nitrogen, 120 parts of ion exchange water, 0.1 part of polyvinyl alcohol, 0.3 part of azobisisobutyronitrile, 34 parts of acrylonitrile, 66 parts of styrene, t-dodecyl mercaptan 0 .3 parts were charged. Then, after polymerization for 5 hours at a reactor temperature of 50 ° C., the temperature was raised to 120 ° C. and reacted for 4 hours, then extracted, washed and dried to obtain a powdery styrene copolymer (H-1A). It was.

(Preparation of styrene copolymer (H-2A))
In a stainless steel polymerization reactor with a nitrogen-substituted stirrer, 0.003 part of sodium dodecylbenzenesulfonate, 28 parts of acrylonitrile, 26 parts of styrene, 36 parts of α-methylstyrene, 10 parts of N-phenylmaleimide, 0.1 part of benzoyl peroxide 7 parts, 0.07 part of t-butyl peroxybenzoate, 0.6 part of calcium phosphate, 0.4 part of t-dodecyl mercaptan, and 120 parts of ion-exchanged water were charged. Then, the temperature of the reactor is raised to 80 ° C., polymerized at this temperature for 8 hours, heated to 120 ° C. and polymerized for 2 hours, then extracted, washed and dried to obtain a powdery styrene copolymer. Combined (H-2A) was obtained.

(Polycarbonate (J-3A))
Polycarbonate (“Iupilon S-3000F” manufactured by Mitsubishi Engineering Plastics) was used as the polycarbonate (J-3A).

"Example 1A"
Graft copolymer (D-1A) 28 parts, styrene copolymer (H-1A) 72 parts, carbon black (Mitsubishi Chemical Co., Ltd., “# 966”) 0.5 part are mixed and a 30 mmφ vacuum vent is mixed. A thermoplastic resin composition (1A) was prepared by melt kneading at a cylinder temperature of 220 ° C. and a vacuum of 93.325 kPa with a twin screw extruder (“Ikegai Co., Ltd.,“ PCM30 ”). The result of having measured MVR of the obtained thermoplastic resin composition (1A) is shown in Table 15A.
Separately, 28 parts of graft copolymer (D-1A), 72 parts of styrene copolymer (H-1A) and 0.8 part of carbon black ("# 966" manufactured by Mitsubishi Chemical Corporation) were mixed, and 30 mmφ was mixed. A thermoplastic resin composition (2A) was prepared by melt kneading at a cylinder temperature of 220 ° C. and a vacuum of 93.325 kPa using a twin-screw extruder with a vacuum vent (“PCM30” manufactured by Ikegai Co., Ltd.).
The obtained thermoplastic resin compositions (1A) and (2A) were each pelletized, various molded products were molded, the flexural modulus was measured, and the impact resistance, glossiness, color developability, and scratch resistance were evaluated. . The results are shown in Table 15A.

"Examples 2A to 26A"
The thermoplastic resin compositions (1A) and (2A) were prepared in the same manner as in Example 1A except that the type of the graft copolymer (D) was changed as shown in Tables 15A to 17A, and MVR was measured. . In addition, various molded products were molded using the obtained thermoplastic resin compositions (1A) and (2A), the flexural modulus was measured, and the impact resistance, glossiness, color development, and scratch resistance were evaluated. . These results are shown in Tables 15A-17A.

"Examples 27A-29A"
As shown in Table 17A, the thermoplastic resin composition (as in Example 1A) was changed except that the type of hard component (J) and the number of parts added were changed and the conditions of melt kneading were changed to 250 ° C. and 93.325 kPa. 1A) and (2A) were prepared, and MVR was measured. In addition, various molded products were molded using the obtained thermoplastic resin compositions (1A) and (2A), the flexural modulus was measured, and the impact resistance, glossiness, color development, and scratch resistance were evaluated. . These results are shown in Table 17A.

“Comparative Examples 1A to 6A”
The thermoplastic resin compositions (1A) and (2A) were prepared in the same manner as in Example 1A, except that the type of the graft copolymer (D) was changed as shown in Table 18A, and MVR was measured. In addition, various molded products were molded using the obtained thermoplastic resin compositions (1A) and (2A), the flexural modulus was measured, and the impact resistance, glossiness, color development, and scratch resistance were evaluated. . These results are shown in Table 18A.

As is clear from Tables 15A to 17A, the thermoplastic resin compositions obtained in the respective examples were excellent in fluidity. In addition, the molded articles obtained in each Example were excellent in impact resistance, glossiness, color development, and scratch resistance.
Therefore, if the graft copolymer (D) in the first aspect of the present invention is used, the thermoplastic resin composition having good fluidity, and excellent in impact resistance and scratch resistance, glossiness and color development are also obtained. An excellent molded product can be obtained and applied to applications such as vehicle interior parts, vehicle exterior parts, office equipment, home appliances, and building materials.

On the other hand, as apparent from Table 18A, a graft copolymer (D) prepared using an ethylene / propylene copolymer (A-2A) having a mass average molecular weight (Mw) of less than 17 × 10 ⁴ as the component (A) In Comparative Example 1A using -2A), the molded article had low impact resistance and scratch resistance.
Comparative Example 2A using a graft copolymer (D-8A) prepared using an ethylene / propylene copolymer (A-8A) having a mass average molecular weight (Mw) exceeding 35 × 10 ⁴ as the component (A) The fluidity of the thermoplastic resin composition was remarkably lowered, and the gloss of the molded product was low.
Comparative Example 3A using a graft copolymer (D-11A) prepared using an ethylene / propylene copolymer (A-11A) having a molecular weight distribution (Mw / Mn) exceeding 3 as component (A) The impact resistance and scratch resistance of the product were low.
In Comparative Example 4A using the graft copolymer (D-15A) prepared using ethylene / propylene / non-conjugated diene copolymer (A-15A) as the component (A), the impact resistance of the molded product was low. It was.
Graft copolymer (D-24A) prepared using crosslinked ethylene / α-olefin copolymer (C-24A) having a gel content of less than 35% by mass as crosslinked ethylene / α-olefin copolymer (C) In Comparative Example 5A using No., the impact resistance, color developability and scratch resistance of the molded product were low.
Graft copolymer (D-31A) prepared by using crosslinked ethylene / α-olefin copolymer (C-31A) having a gel content of more than 75% by mass as crosslinked ethylene / α-olefin copolymer (C) In Comparative Example 6A using No., the impact resistance and scratch resistance of the molded product were low.

<Measurement method 2 of volume average particle diameter>
The volume average particle diameter (MV) was measured using a microtrack (“Nanotrack 150” manufactured by Nikkiso Co., Ltd.) using pure water as a measurement solvent.
The volume of the ethylene / α-olefin copolymer (A) dispersed in the aqueous olefin resin dispersion (B) and the volume of the crosslinked ethylene / α-olefin copolymer (C) dispersed in the aqueous dispersion are as follows. The average particle diameter shows the volume average particle diameter of the ethylene / α-olefin copolymer (A) or the crosslinked ethylene / α-olefin copolymer (C) in the thermoplastic resin composition as it is. Confirmed by image analysis.

<Melting and kneading 3>
Graft copolymer (D), methacrylic ester resin (G), and other components as required are mixed in the formulations shown in Tables 22B to 31B, and a twin screw extruder with a 30 mmφ vacuum vent (“PCM30 manufactured by Ikegai Co., Ltd.) )) Was melt kneaded at a cylinder temperature of 200 to 260 ° C. and a vacuum of 93.325 kPa to obtain a thermoplastic resin composition. Moreover, after melt-kneading as needed, pelletization was performed using a pelletizer (“SH type pelletizer” manufactured by Souken Co., Ltd.).

<Injection molding 3>
The pellets of the thermoplastic resin composition obtained by melt kneading are subjected to bending elasticity with an injection molding machine (“IS55FP-1.5A” manufactured by Toshiba Machine Co., Ltd.) under conditions of a cylinder temperature of 200 to 260 ° C. and a mold temperature of 60 ° C. Test pieces for rate and Charpy impact tests were obtained, 2 mm thick flat plates (10 cm × 10 cm).

<Evaluation of impact resistance: Charpy impact test>
The test piece was subjected to a Charpy impact test (notched) at 23 ° C. in accordance with ISO 179 standard, and the Charpy impact strength was measured.

<Evaluation of heat resistance>
Based on the ISO test method 75 standard, the deflection temperature (° C.) under load was measured by 1.83 MPa, 4 mm, and the flatwise method.

<Glossiness evaluation 2>
The gloss of the 2 mm thick flat plate was measured with a digital variable gloss meter (“UGV-5D” manufactured by Suga Test Instruments Co., Ltd.) under conditions of an incident angle of 60 ° and a reflection angle of 60 °.

<Evaluation of color development>
100 parts of the thermoplastic resin composition was mixed with 0.8 parts of carbon black and colored, and a black colored plate (molded product (Ma)) of 100 × 100 mm (thickness 2 mm) was obtained by injection molding. .
For the molded product (Ma), the lightness L ^* was measured by a SCE method using a spectrocolorimeter (“CM-3500d” manufactured by Konica Minolta Optips). The L ^* measured in this way is referred to as “L ^* (ma)”. The lower L ^* , the more black and the better the color developability.

<Evaluation of scratch resistance>
Using a pencil hardness tester, a pencil with a hardness of 3H was pressed against the surface of the molded product (Ma) with a load of 750 g, and the molded product (Ma) was moved by about 5 cm in this state, whereby the molded product (Ma) The surface was scratched with a pencil to scratch the molded product (Ma). The brightness L ^* of the surface of the scratched molded article (Mb) was measured by the SCE method using a spectrocolorimeter. The L ^* measured in this way is referred to as “L ^* (mb)”.

(Scratch resistance determination 1)
A determination index ΔL ^* of the degree of conspicuousness of scratches on the molded product (Mb) was calculated from the following formula (3). As the absolute value of ΔL ^* (mb−ma) is larger, scratches are more conspicuous.
ΔL ^* (mb−ma) = L ^* (mb) −L ^* (ma) (3)

When the absolute value of ΔL ^* (mb−ma) is 3.0 or less, scratches are not noticeable and the design of the molded product is not impaired.
When the absolute value of ΔL ^* (mb−ma) is more than 3.0 to 7.0 or less, scratches are not noticeable and the design of the molded product is not impaired.
When the absolute value of ΔL ^* (mb−ma) is more than 7.0, scratches are conspicuous and the design of the molded product is impaired.

(Scratch resistance determination 2)
Using a shape measurement laser microscope ("VK-9700" manufactured by Keyence Corporation) as an index for determining the ease of scratches on the molded product (Ma), the 10-point average roughness (Rz jis) of the molded product (Mb) is used. It was measured. The larger the value of Rz jis, the easier it is to scratch.

<Evaluation of scratch resistance>
As shown in FIG. 1, a rod-like jig 10 having a tip portion 11 formed in a hemispherical shape was prepared, and the tip portion 11 was covered with a laminated sheet 12 in which eight sheets of gauze were stacked. The tip part 11 covered with the laminated sheet 12 is brought into contact with the surface of the molded product (Ma) 13 so that the rod-shaped jig 10 is at a right angle, and the tip part 11 is brought into contact with the surface of the molded product (Ma) 13. Were slid in the horizontal direction (arrow direction in the figure) and reciprocated 100 times. At that time, the applied load was 1 kg. After reciprocating 100 times, the lightness L ^* of the surface of the scratched molded article (Mc) was measured by the SCE method using a spectrocolorimeter. The L ^* measured in this way is referred to as “L ^* (mc)”.

(Abrasion resistance judgment 1)
A determination index ΔL ^* of the degree of conspicuousness of scratches on the molded article (Mc) was calculated from the following formula (4). As the absolute value of ΔL ^* (mc−ma) is larger, the scratches are more conspicuous.
ΔL ^* (mc−ma) = L * (mc) −L * (ma) (4)

When the absolute value of ΔL ^* (mc−ma) is 3.0 or less, scratches are not noticeable and the design of the molded product is not impaired.
When the absolute value of ΔL ^* (mc−ma) is more than 3.0 to 7.0 or less, scratches are not noticeable and the design of the molded product is not impaired.
When the absolute value of ΔL ^* (mc−ma) is more than 7.0, scratches are conspicuous and the design of the molded product is impaired.

(Scratch resistance determination 2)
Measure the 10-point average roughness (Rz jis) of a molded product (Mc) with a shape measurement laser microscope (VK-9700, manufactured by Keyence Corporation) as an index for determining the ease of scratches on the molded product (Ma). did. The larger the value of Rz jis, the easier it is to scratch.

<Each component>
In the following examples, the following ethylene / α-olefin copolymer (A), olefin resin aqueous dispersion (B), crosslinked ethylene / α-olefin copolymer (C), graft copolymer (D), methacryl An acid ester resin (G) and a styrene copolymer (H) were used.

<Ethylene / α-olefin copolymer (A)>
(Preparation of ethylene / propylene copolymer (A-1B))
After fully substituting the stainless polymerization tank equipped with a 20 L stirrer with nitrogen, 10 L of dehydrated and purified hexane was added, and ethylaluminum sesquichloride (Al (C ₂ H ₅ ) _1.5 · Cl ₁ prepared to 8.0 mmol / L was added. ₅ ) was continuously supplied at a rate of 5 L / h for 1 hour, and then a hexane solution of VO (OC ₂ H ₅ ) Cl ₂ adjusted to 0.8 mmol / L as a catalyst was further added to 5 L / h. Hexane was continuously fed in an amount of 5 L / h. On the other hand, from the upper part of the polymerization tank, the polymerization liquid was continuously extracted so that the polymerization liquid in the polymerization tank was always 10 L. Using a bubbling tube, ethylene was supplied in an amount of 2000 L / h, propylene was supplied in an amount of 1000 L / h, hydrogen was supplied in an amount of 8 L / h, and a polymerization reaction was performed at 35 ° C.
A polymerization reaction was performed under the above conditions to obtain a polymerization solution containing an ethylene / propylene copolymer (A-1B). The obtained polymerization solution was deashed with hydrochloric acid, poured into methanol for precipitation, and then dried to obtain an ethylene / propylene copolymer (A-1B). Table 1 shows the properties of the ethylene / propylene copolymer (A-1B).

(Preparation of ethylene / propylene copolymers (A-2B) to (A-8B))
The ethylene / propylene copolymers (A-2B) to (A-) were the same as the ethylene / propylene copolymers (A-1B) except that the hydrogen supply amount was changed as shown in Tables 1B and 2B. 8B) was obtained. The properties of the ethylene / propylene copolymers (A-2B) to (A-8B) are shown in Tables 1B and 2B.

(Preparation of ethylene / propylene copolymer (A-9B))
After sufficiently substituting a 20 L stainless steel tank with a stirrer with nitrogen, 10 L of dehydrated and purified hexane was added, and 110 L of propylene (standard state) and 800 mL of hydrogen were added. After heating to 40 ° C., it was pressurized with ethylene so that the total pressure was 0.6 MPa [gage].
When the internal pressure reached 0.6 MPa [gage], 10 mL of a 1.0 mM / mL hexane solution of triisobutylaluminum (TIBA) was injected with nitrogen. Triphenylcarbenium (tetrakispentafluorophenyl) borate prepared in advance was 0.16 mM in terms of boron, and [dimethyl (t-butylamide) (tetramethyl-η5-cyclopentadienyl) silane] titanium chloride was changed to 0. Polymerization was initiated by injecting 30 mL of a toluene solution containing 0004 mM with nitrogen. Thereafter, the temperature was adjusted to 40 ° C. for 5 minutes, and ethylene was supplied so that the pressure became 0.6 MPa [gage]. Five minutes after the start of the polymerization, 50 mL of methanol was inserted to stop the polymerization, and the pressure was released to atmospheric pressure to obtain a polymerization solution containing an ethylene / propylene copolymer (A-9B). The obtained polymerization solution was deashed with hydrochloric acid, poured into methanol for precipitation, and then dried to obtain an ethylene / propylene copolymer (A-9B). Properties of the ethylene / propylene copolymer (A-9B) polymer are shown in Table 4B.

(Preparation of ethylene / propylene copolymer (A-10B))
20 parts of ethylene / propylene copolymer (A-1B) and 80 parts of ethylene / propylene copolymer (A-9B) are mixed and a twin screw extruder with a 30 mmφ vacuum vent (“PCM30” manufactured by Ikekai Co., Ltd.) The mixture was melt-kneaded at 200 ° C. and 93.325 kPa vacuum to prepare an ethylene / propylene copolymer (A-10B). Table 4B shows the properties of the ethylene / propylene copolymer (A-10B) polymer.

(Preparation of ethylene / propylene copolymer (A-11B))
An ethylene / propylene copolymer (A-11B) is obtained in the same manner as the ethylene / propylene copolymer (A-1B) except that VCl ₄ is used instead of VO (OC ₂ H ₅ ) Cl ₂ as a catalyst. It was. Table 2B shows the polymer properties of the ethylene / propylene copolymer (A-11B).

(Preparation of ethylene / propylene copolymer (A-12B))
Mixing 75 parts of ethylene / propylene copolymer (A-1B) and 25 parts of ethylene / propylene copolymer (A-11B), twin screw extruder with 30 mmφ vacuum vent (“PCM30” manufactured by Ikegai Co., Ltd.) The mixture was melt kneaded at 200 ° C. and 93.325 kPa vacuum to prepare an ethylene / propylene copolymer (A-12B). Table 4B shows the polymer properties of the ethylene / propylene copolymer (A-12B).

(Preparation of ethylene / propylene copolymer (A-13B))
Mixing 50 parts of ethylene / propylene copolymer (A-1B) and 50 parts of ethylene / propylene copolymer (A-11B), twin screw extruder with 30 mmφ vacuum vent (“PCM30”, manufactured by Ikegai Co., Ltd.) The mixture was melt kneaded at 200 ° C. and 93.325 kPa vacuum to prepare an ethylene / propylene copolymer (A-13B). Properties of the ethylene / propylene copolymer (A-13B) polymer are shown in Table 4B.

(Preparation of ethylene / propylene copolymer (A-14B))
20 parts of ethylene / propylene copolymer (A-1B) and 80 parts of ethylene / propylene copolymer (A-11B) are mixed, and a twin screw extruder with a 30 mmφ vacuum vent (“PCM30” manufactured by Ikekai Co., Ltd.) Was melt-kneaded at 200 ° C. and 93.325 kPa vacuum to prepare an ethylene / propylene copolymer (A-14B). Table 4B shows the polymer properties of the ethylene / propylene copolymer (A-14B).

(Preparation of ethylene / propylene copolymers (A-15B) to (A-20B))
As shown in Table 3B, the ethylene / propylene copolymers (A-15B) to (A-15B) to (A) are the same as the ethylene / propylene copolymers (A-1B) except that the supply amounts of ethylene, propylene and hydrogen are changed. -20B) was obtained. Properties of the ethylene / propylene copolymers (A-15B) to (A-20B) are shown in Table 3B.

<Olefin resin aqueous dispersion (B)>
(Preparation of aqueous dispersion of olefin resin (B-1B))
100 parts of an ethylene / propylene copolymer (A-1B) and maleic anhydride-modified polyethylene (“Mitsui Chemicals,“ Mitsui High Wax 2203A ”) as the acid-modified olefin polymer, mass average molecular weight: 2,700, acid value: 30 mg / g) 20 parts and 4 parts of potassium oleate as an anionic emulsifier were mixed.
While supplying this mixture at 4 kg / h from a hopper of a twin screw extruder (Ikegai, “PCM30”, L / D = 40) and continuously supplying a 14% potassium hydroxide aqueous solution at 240 g / h. The mixture was melt-kneaded by heating to 220 ° C., and the resulting melt-kneaded product was extruded. The melt-kneaded product was continuously supplied to a cooling device attached to the tip of the extruder and cooled to 90 ° C. The taken-out solid was poured into warm water at 80 ° C. and continuously dispersed to obtain an aqueous olefin resin dispersion (B-1B) having a volume average particle size of 0.25 μm.

(Preparation of aqueous olefin resin dispersions (B-2B) to (B-20B))
As shown in Table 2B, the olefin resin was the same as the aqueous olefin resin dispersion (B-1B) except that (A-1B) was changed to (A-2B) to (A-20B) as the component A. Aqueous dispersions (B-2B) to (B-20B) were obtained.
Tables 5B to 7B show the volume average particle diameters of the ethylene / α-olefin copolymers (A) dispersed in the respective olefin resin aqueous dispersions (B-1B) to (B-20B).

<Crosslinked ethylene / α-olefin copolymer (C)>
(Preparation of crosslinked ethylene / α-olefin copolymer (C-1B))
Ion exchange water was added to the olefin resin aqueous dispersion (B-1B) (100 parts as a solid content) to a solid content concentration of 35%, and 0.5 parts of t-butylcumyl peroxide as an organic peroxide, As a polyfunctional compound, 1 part of divinylbenzene was added and reacted at 130 ° C. for 5 hours to prepare a crosslinked ethylene / α-olefin copolymer (C-1B). The gel content of the crosslinked ethylene / α-olefin copolymer (C-1B) was measured and found to be 51%. The results are shown in Table 8B.

(Preparation of crosslinked ethylene / α-olefin copolymers (C-2B) to (C-15B))
As shown in Table 8B, the same procedure as for the crosslinked ethylene / α-olefin copolymer (C-1B) except that the type of the aqueous olefin resin dispersion (B) and the addition amount of t-butylcumyl peroxide were changed. As a result, crosslinked ethylene / α-olefin copolymers (C-2B) to (C-15B) were obtained. The gel contents of the crosslinked ethylene / α-olefin copolymers (C-2B) to (C-15B) are shown in Table 8B.

(Adjustment of crosslinked ethylene / α-olefin copolymer (C-16B) to (C-24B))
As shown in Table 9B and Table 10B, except that the addition amount of t-butylcumyl peroxide was changed, the crosslinked ethylene / α-olefin copolymer was the same as the crosslinked ethylene / α-olefin copolymer (C-1B). Polymers (C-16B) to (C-24B) were obtained. The gel contents of the crosslinked ethylene / α-olefin copolymers (C-16B) to (C-24B) are shown in Table 9B and Table 10B.

<Graft copolymer (D)>
(Preparation of graft copolymer (D-1B))
An aqueous olefin resin dispersion (B-1B) (70 parts as a solid content of ethylene / propylene copolymer (A-1B)) is placed in a stainless polymerization tank equipped with a stirrer, and an aqueous olefin resin dispersion (B-1B). Ion-exchanged water was added to the solution so that the solid concentration was 30%, and 0.006 part of ferrous sulfate, 0.3 part of sodium pyrophosphate and 0.35 part of fructose were added, and the temperature was set to 80 ° C. Styrene (23.4 parts), acrylonitrile (6.6 parts) and cumene hydroperoxide (0.6 parts) were continuously added for 150 minutes, and the polymerization temperature was kept at 80 ° C. to carry out emulsion polymerization. After the polymerization, an antioxidant is added to the aqueous dispersion containing the graft copolymer (D-1B), solids are precipitated with sulfuric acid, and after washing, dehydration and drying, A polymer (D-1B) was obtained. The graft ratio of the graft copolymer (D-1B) was measured and found to be 30%. The results are shown in Table 11B.

(Preparation of graft copolymers (D-2B) to (D-14B))
As shown in Table 11B to Table 14B, except that the type of the aqueous olefin resin dispersion (B) was changed, the graft copolymer (D-2B) to (D-2B) to ( D-14B) was obtained. The graft ratios of the graft copolymers (D-2B) to (D-14B) are shown in Tables 11B to 14B.

(Preparation of graft copolymer (D-15B))
A stainless polymerization tank equipped with a stirrer was charged with 70 parts of ethylene / propylene copolymer (A-1B) and 300 parts of toluene, and the contents were stirred at 70 ° C. for 1 hour to uniformly dissolve. After sufficiently purging with nitrogen, 23.4 parts of styrene, 6.6 parts of acrylonitrile, 0.24 parts of t-dodecyl mercaptan and 0.22 parts of t-butylperoxyisopropyl monocarbonate were added, and the internal temperature was 110 ° C. The mixture was heated up to react for 4 hours. The internal temperature was raised to 120 ° C. and reacted for 2 hours. After the polymerization, the internal temperature was cooled to 100 ° C., and 0.2 part of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenol) -propionate was added. The reaction mixture was extracted, and unreacted substances and the solvent were distilled off by steam distillation. The volatile matter was substantially devolatilized at 220 ° C. and 93.325 kPa vacuum using a twin screw extruder with a 30 mmφ vacuum vent (“PCM30” manufactured by Ikegai Co., Ltd.), pelletized, and graft copolymer (D-15B ) The graft ratio of the graft copolymer (D-15B) was measured and found to be 26%. The results are shown in Table 14B.

(Preparation of graft copolymers (D-16B) to (D-39B))
As shown in Tables 15B to 18B, the graft copolymer (D-1) except that the aqueous olefin resin dispersion (B-1B) was changed to an aqueous dispersion containing a crosslinked ethylene / α-olefin copolymer (C). In the same manner as in (-1B), graft copolymers (D-16B) to (D-39B) were obtained. The graft ratios of the graft copolymers (D-16B) to (D-39B) are shown in Tables 15B to 18B.

<Methacrylate ester resin (G)>
(Preparation of methacrylic ester resin (G-1B))
In a stainless steel polymerization tank equipped with a stirrer, 150 parts of ion exchange water, 99 parts of methyl methacrylate, 1 part of methyl acrylate, 0.2 part of 2,2′-azobis (isobutyronitrile), 0.25 part of n-octyl mercaptan , 0.47 part of calcium hydroxyapatite and 0.003 part of potassium alkenyl succinate were charged. The internal temperature of the polymerization tank was set to 75 ° C. for 3 hours, and the temperature was raised to 90 ° C. for 1 hour. The contents were extracted, washed with a centrifugal dehydrator, and dried to obtain a powdery methacrylic ester resin (G-1B). The monomers are shown in Table 19B.

(Preparation of methacrylic ester resin (G-2B))
In a stainless polymerization tank equipped with a stirrer, 150 parts of ion exchange water, 82 parts of methyl methacrylate, 12 parts of N-phenylmaleimide, 6 parts of styrene, 0.2 part of 2,2′-azobis (isobutyronitrile), n-octyl Mercaptan (0.25 part) and polyvinyl alcohol (0.7 part) were charged. The internal temperature of the polymerization tank was set at 75 ° C. for 3 hours, and the temperature was raised to 90 ° C. for 1 hour. The contents were extracted, washed with a centrifugal dehydrator, and dried to obtain a powdery methacrylate resin (G-2B). The monomers are shown in Table 19B.

(Preparation of methacrylate resin (G-3B) to (G-11B))
As shown in Table 19B and Table 20B, except for changing the kind of the vinyl monomer mixture (m3), the same procedure as for the methacrylate ester resin (G-2B), the methacrylate ester resin (G-3B) to (G-11B) was obtained.

<Styrene copolymer (H)>
(Preparation of styrene copolymer (H-1B))
In a stainless steel polymerization tank equipped with a stirrer substituted with nitrogen, 120 parts of ion exchange water, 0.1 part of polyvinyl alcohol, 0.3 part of 2,2′-azobis (isobutyronitrile), 25 parts of acrylonitrile, 75 parts of styrene, t -0.35 part of dodecyl mercaptan was charged and reacted at an initial temperature of 60 ° C for 5 hours. The temperature was raised to 120 ° C. and reacted for 4 hours. The contents were taken out to obtain a styrene copolymer (H-1B).

(Preparation of styrene copolymer (H-2B))
In a stainless steel polymerization tank equipped with a stirrer, 150 parts of ion exchange water, 7 parts of methyl methacrylate, 23 parts of acrylonitrile, 70 parts of styrene, 0.2 part of 2,2′-azobis (isobutyronitrile), n-octyl mercaptan 0 .25 parts, calcium hydroxyapatite 0.47 part, and potassium alkenyl succinate 0.003 part were charged, the internal temperature was raised to 75 ° C., and the reaction was performed for 3 hours. The reaction was completed by raising the temperature to 90 ° C. and holding for 60 minutes. The contents were taken out, repeatedly washed with a centrifugal dehydrator, dehydrated, and dried to obtain a styrene copolymer (H-2B).

(Preparation of styrenic copolymers (H-3B) to (H-6B))
As shown in Table 21B, except that the amount of the vinyl monomer mixture (m4) was changed, the styrene copolymer (H-3B) to (H-3B) to ( H-6B) was obtained.

[Example 1B]
24 parts of graft copolymer (D-1B) and 76 parts of methacrylic ester resin (G-1B) were mixed, and 240 ° C., 93 ° C. using a 30 mmφ twin-screw extruder with a vacuum vent (“Ikegai Co., Ltd.,“ PCM30 ”) A thermoplastic resin composition was prepared by melt kneading in a vacuum of 325 kPa. The MVR of the thermoplastic resin composition is shown in Table 22B.
The thermoplastic resin composition was pelletized, various molded products were molded, the flexural modulus was measured, and the impact resistance, heat resistance, glossiness, color development, scratch resistance, and scratch resistance were evaluated. The results are shown in Table 22B.

[Examples 2B to 33B]
A thermoplastic resin composition was prepared and MVR was measured in the same manner as in Example 1B except that the type of graft copolymer (D) was changed as shown in Tables 22B to 27B.
The thermoplastic resin composition was pelletized, various molded products were molded, the flexural modulus was measured, and the impact resistance, heat resistance, glossiness, color development, scratch resistance, and scratch resistance were evaluated. The results are shown in Tables 22B to 27B.

[Examples 34B to 56B]
As shown in Tables 28B to 31B, the types and amounts of the graft copolymer (D), the methacrylic ester resin (G), and the styrene copolymer (H) were changed, and the melt kneading conditions were 250 ° C., 93 A thermoplastic resin composition was prepared and MVR was measured in the same manner as in Example 1B except that the pressure was changed to .325 kPa.
The thermoplastic resin composition was pelletized, various molded products were molded, the flexural modulus was measured, and the impact resistance, heat resistance, glossiness, color development, scratch resistance, and scratch resistance were evaluated. The results are shown in Tables 28B to 31B.

[Comparative Examples 1B to 6B]
A thermoplastic resin composition was prepared and MVR was measured in the same manner as in Example 1B, except that the type of the graft copolymer (D) was changed as shown in Table 32B.
The thermoplastic resin composition was pelletized, various molded products were molded, the flexural modulus was measured, and the impact resistance, heat resistance, glossiness, color development, scratch resistance, and scratch resistance were evaluated. The results are shown in Table 32B.

The thermoplastic resin compositions of Examples 1B to 56B were excellent in fluidity. In addition, the molded products obtained in Examples 1B to 56B were excellent in impact resistance, heat resistance, gloss, color development, scratch resistance, and scratch resistance.
Therefore, the thermoplastic resin composition according to the third aspect of the present invention has excellent fluidity, and when the thermoplastic resin composition according to the third aspect of the present invention is used, impact resistance, glossiness, color developability. It can be seen that a molded article excellent in scratch resistance and scratch resistance is obtained, and can be applied to uses such as vehicle interior parts, vehicle exterior parts, office equipment, home appliances, and building materials.

On the other hand, Comparative Example 1B using an ethylene / propylene copolymer (A-2B) having a mass average molecular weight (Mw) of less than 17 × 10 ⁴ as the ethylene / α-olefin copolymer (A) Impact and scratch resistance were low.
Comparative Example 2B using an ethylene / propylene copolymer (A-8B) having a mass average molecular weight (Mw) exceeding 35 × 10 ⁴ as the ethylene / α-olefin copolymer (A) is a thermoplastic resin composition. The fluidity was significantly reduced and the gloss of the molded product was low.
Comparative example 3B using an ethylene / propylene copolymer (A-11B) having a molecular weight distribution (Mw / Mn) of more than 3 as the ethylene / α-olefin copolymer (A) is used for the impact resistance, Scratch resistance was low.
Comparative Example 4B using a crosslinked ethylene / α-olefin copolymer (C-2B) obtained by crosslinking an ethylene / propylene copolymer (A-2B) as the crosslinked ethylene / α-olefin copolymer (C) is: The impact resistance and scratch resistance of the molded product were low.
Comparative Example 5B using a crosslinked ethylene / α-olefin copolymer (C-5B) obtained by crosslinking an ethylene / propylene copolymer (A-8B) as the crosslinked ethylene / α-olefin copolymer (C) is: The fluidity of the thermoplastic resin composition was remarkably lowered, and the gloss of the molded product was low.
Comparative Example 6B using a crosslinked ethylene / α-olefin copolymer (C-8B) obtained by crosslinking the ethylene / propylene copolymer (A-11B) as the crosslinked ethylene / α-olefin copolymer (C) is: The impact resistance and scratch resistance of the molded product were low.

<Measurement method 2 of volume average particle diameter>
The volume average particle diameter (MV) was measured using a microtrack (“Nanotrack 150” manufactured by Nikkiso Co., Ltd.) using pure water as a measurement solvent.
The ethylene / α-olefin copolymer (A) dispersed in the aqueous olefin resin dispersion (B), the crosslinked ethylene / α-olefin copolymer (C) dispersed in the aqueous dispersion, The volume average particle diameter of the crosslinked acrylic ester rubber-like polymer (E) dispersed in the aqueous dispersion is the same as that of the ethylene / α-olefin copolymer (A) or the crosslinked ethylene / polymer in the thermoplastic resin composition. It has been confirmed by electron microscope image analysis that the volume average particle diameters of the α-olefin copolymer (C) and the crosslinked acrylate rubber polymer (E) are shown.

<Melt-kneading 4>
Graft copolymer (D), graft copolymer (F), methacrylic ester resin (G), and other components as necessary are mixed in the formulations shown in Table 24C to Table 35C, and a vacuum vent with 30 mmφ 2 A thermoplastic resin composition was obtained by melt kneading in a shaft extruder (“PCM30” manufactured by Ikegai Co., Ltd.) at a cylinder temperature of 200 to 260 ° C. and a vacuum of 93.325 kPa. Moreover, after melt-kneading as needed, pelletization was performed using a pelletizer (“SH type pelletizer” manufactured by Souken Co., Ltd.).

<Injection molding 4>
The pellets of the thermoplastic resin composition obtained by melt kneading are subjected to Charpy impact using an injection molding machine (“IS55FP-1.5A” manufactured by Toshiba Machine Co., Ltd.) at a cylinder temperature of 200 to 260 ° C. and a mold temperature of 60 ° C. A test specimen for test, a 2 mm-thick flat plate (10 cm × 10 cm) was obtained.

<Each component>
In the following examples, the following ethylene / α-olefin copolymer (A), olefin resin aqueous dispersion (B), crosslinked ethylene / α-olefin copolymer (C), graft copolymer (D), crosslinked An acrylic ester rubbery polymer (E), a graft copolymer (F), a methacrylic ester resin (G), and a styrene copolymer (H) were used.

<Ethylene / α-olefin copolymer (A)>
(Preparation of ethylene / propylene copolymer (A-1C))
After fully substituting the stainless steel polymerization tank with a 20 L stirrer with nitrogen, 10 L of dehydrated and purified hexane was added, and ethylaluminum sesquichloride (Al (C ₂ H ₅ ) _1.5 · C ₁₁ was prepared to 8.0 mmol / L. ₅ ) was continuously supplied at a rate of 5 L / h for 1 hour, and then a hexane solution of VO (OC ₂ H ₅ ) Cl ₂ adjusted to 0.8 mmol / L as a catalyst was further added to 5 L / h. Hexane was continuously fed in an amount of 5 L / h. On the other hand, from the upper part of the polymerization tank, the polymerization liquid was continuously extracted so that the polymerization liquid in the polymerization tank was always 10 L. Using a bubbling tube, ethylene was supplied in an amount of 2000 L / h, propylene was supplied in an amount of 1000 L / h, hydrogen was supplied in an amount of 8 L / h, and a polymerization reaction was performed at 35 ° C.
A polymerization reaction was performed under the above conditions to obtain a polymerization solution containing an ethylene / propylene copolymer (A-1C). The obtained polymerization solution was deashed with hydrochloric acid, poured into methanol for precipitation, and then dried to obtain an ethylene / propylene copolymer (A-1C). Table 1 shows the properties of the ethylene / propylene copolymer (A-1C) polymer.

(Preparation of ethylene / propylene copolymers (A-2C) to (A-5C))
The ethylene / propylene copolymers (A-2C) to (A-5C) were prepared in the same manner as the ethylene / propylene copolymer (A-1C) except that the amount of hydrogen supplied was changed as shown in Table 1C. Obtained. Properties of the ethylene / propylene copolymers (A-2C) to (A-5C) are shown in Table 1C.

(Preparation of ethylene / propylene copolymer (A-6C))
After sufficiently substituting a 20 L stainless steel tank with a stirrer with nitrogen, 10 L of dehydrated and purified hexane was added, and 110 L of propylene (standard state) and 800 mL of hydrogen were added. After heating to 40 ° C., it was pressurized with ethylene so that the total pressure was 0.6 MPa [gage].
When the internal pressure reached 0.6 MPa [gage], 10 mL of a 1.0 mM / mL hexane solution of triisobutylaluminum (TIBA) was injected with nitrogen. Triphenylcarbenium (tetrakispentafluorophenyl) borate prepared in advance was 0.16 mM in terms of boron, and [dimethyl (t-butylamide) (tetramethyl-η5-cyclopentadienyl) silane] titanium chloride was changed to 0. Polymerization was initiated by injecting 30 mL of a toluene solution containing 0004 mM with nitrogen. Thereafter, the temperature was adjusted to 40 ° C. for 5 minutes, and ethylene was supplied so that the pressure became 0.6 MPa [gage]. Five minutes after the start of the polymerization, 50 mL of methanol was inserted to terminate the polymerization, and the pressure was released to atmospheric pressure to obtain a polymerization solution containing an ethylene / propylene copolymer (A-6C). The obtained polymerization solution was deashed with hydrochloric acid, poured into methanol for precipitation, and then dried to obtain an ethylene / propylene copolymer (A-6C). Properties of the ethylene / propylene copolymer (A-6C) polymer are shown in Table 2C.

(Preparation of ethylene / propylene copolymer (A-7C))
20 parts of ethylene / propylene copolymer (A-1C) and 80 parts of ethylene / propylene copolymer (A-6C) are mixed, and a twin screw extruder with a 30 mmφ vacuum vent (“PCM30” manufactured by Ikegai Co., Ltd.) The mixture was melt kneaded at 200 ° C. and 93.325 kPa vacuum to prepare an ethylene / propylene copolymer (A-7C). Table 2C shows the properties of the ethylene / propylene copolymer (A-7C) polymer.

(Preparation of ethylene / propylene copolymer (A-11C))
An ethylene / propylene copolymer (A-11C) is obtained in the same manner as the ethylene / propylene copolymer (A-1C) except that VCl ₄ is used instead of VO (OC ₂ H ₅ ) Cl ₂ as a catalyst. It was. Table 1C shows the properties of the ethylene / propylene copolymer (A-11C) polymer.

(Preparation of ethylene / propylene copolymer (A-8C))
Mixing 75 parts of ethylene / propylene copolymer (A-1C) and 25 parts of ethylene / propylene copolymer (A-11C), twin screw extruder with 30 mmφ vacuum vent (“PCM30” manufactured by Ikegai Co., Ltd.) And kneaded at 200 ° C. and 93.325 kPa vacuum to prepare an ethylene / propylene copolymer (A-8C). The properties of the ethylene / propylene copolymer (A-8C) polymer are shown in Table 2C.

(Preparation of ethylene / propylene copolymer (A-9C))
Mixing 50 parts of ethylene / propylene copolymer (A-1C) and 50 parts of ethylene / propylene copolymer (A-11C), twin screw extruder with 30 mmφ vacuum vent (Ikegai, “PCM30”) The mixture was melt kneaded at 200 ° C. and 93.325 kPa vacuum to prepare an ethylene / propylene copolymer (A-9C). The properties of the ethylene / propylene copolymer (A-9C) polymer are shown in Table 2C.

(Preparation of ethylene / propylene copolymer (A-10C))
20 parts of ethylene / propylene copolymer (A-1C) and 80 parts of ethylene / propylene copolymer (A-11C) are mixed and a twin screw extruder with a 30 mmφ vacuum vent (“PCM30” manufactured by Ikekai Co., Ltd.) Was melt-kneaded at 200 ° C. and 93.325 kPa vacuum to prepare an ethylene / propylene copolymer (A-10C). Properties of the ethylene / propylene copolymer (A-10C) polymer are shown in Table 2C.

(Preparation of ethylene / propylene copolymers (A-12C) and (A-13C))
The ethylene / propylene copolymers (A-12C) and (A-13C) were prepared in the same manner as the ethylene / propylene copolymer (A-1C) except that the supply amount of hydrogen was changed as shown in Table 3C. Obtained. Table 3C shows the properties of the ethylene / propylene copolymers (A-12C) and (A-13C).

<Olefin resin aqueous dispersion (B)>
(Preparation of aqueous dispersion of olefin resin (B-1C))
100 parts of ethylene / propylene copolymer (A-1C) and maleic anhydride-modified polyethylene (Mitsui Chemicals, “Mitsui High Wax 2203A”) as an acid-modified olefin polymer, weight average molecular weight: 2,700, acid value: 30 mg / g) 20 parts and 5 parts of potassium oleate as an anionic emulsifier were mixed.
This mixture is supplied at 4 kg / h from a hopper of a twin screw extruder (Ikegai, “PCM30”, L / D = 40), and water is supplied from a supply port provided in a vent portion of the twin screw extruder. While continuously supplying an aqueous solution obtained by mixing 0.5 part of potassium oxide and 2.4 parts of ion-exchanged water, it was heated to 220 ° C., melt-kneaded and extruded. The melt-kneaded product was continuously supplied to a cooling device attached to the tip of the twin screw extruder and cooled to 90 ° C. Then, the solid discharged from the tip of the twin screw extruder is poured into warm water at 80 ° C., continuously dispersed, diluted to a solid content concentration of about 40% by mass, and an aqueous olefin resin dispersion (B -1C) was obtained.
Table 4C shows the volume average particle diameter of the ethylene / α-olefin copolymer (A) dispersed in the aqueous olefin resin dispersion (B-1C).

(Preparation of aqueous olefin resin dispersions (B-2C) to (B-11C))
As shown in Table 4C and Table 5C, the same procedure as in the aqueous olefin resin dispersion (B-1C) was conducted except that (A-1C) was changed from (A-2C) to (A-11C) as the component A. Thus, aqueous olefin resin dispersions (B-2C) to (B-11C) were obtained.
Tables 4C and 5C show the volume average particle diameters of the ethylene / α-olefin copolymers (A) dispersed in each of the aqueous olefin resin dispersions (B-2C) to (B-11C).

(Preparation of aqueous olefin resin dispersions (B-12C) to (B-17C))
As shown in Table 5C, the aqueous olefin resin dispersion was the same as the aqueous olefin resin dispersion (B-1C) except that the number of added parts of potassium hydroxide during emulsification and the number of added parts of ion exchange water were changed. (B-12C) to (B-17C) were obtained.
Table 5C shows the volume average particle diameter of the ethylene / α-olefin copolymer (A) dispersed in each of the aqueous olefin resin dispersions (B-12C) to (B-17C).

(Preparation of aqueous dispersion of olefin resin (B-18C) and (B-19C))
As shown in Table 6C, the olefin resin was the same as the aqueous olefin resin dispersion (B-1C) except that (A-1C) was changed to (A-12C) and (A-13C) as the A component. Aqueous dispersions (B-18C) and (B-19C) were obtained.
Table 6C shows the volume average particle size of the ethylene / α-olefin copolymer (A) dispersed in each of the aqueous olefin resin dispersions (B-18C) and (B-19C).

<Crosslinked ethylene / α-olefin copolymer (C)>
(Preparation of cross-linked ethylene / α-olefin copolymer (C-1C))
Ion exchange water was added to the olefin resin aqueous dispersion (B-1C) (100 parts as a solid content) to a solid content concentration of 35%, and 0.5 parts of t-butylcumyl peroxide as an organic peroxide, As a polyfunctional compound, 1 part of divinylbenzene was added and reacted at 130 ° C. for 5 hours to prepare a crosslinked ethylene / α-olefin copolymer (C-1C). Table 7C shows the gel content and volume average particle size of the crosslinked ethylene / α-olefin copolymer (C-1C).

(Preparation of crosslinked ethylene / α-olefin copolymers (C-2C) to (C-14C))
As shown in Table 7C and Table 8C, the cross-linked ethylene / α-olefin copolymer (C-1C) and the olefin resin aqueous dispersion (B) and the addition amount of t-butylcumyl peroxide were changed except that Similarly, crosslinked ethylene / α-olefin copolymers (C—C2) to (C-14C) were obtained. Tables 7C and 8C show the gel contents and volume average particle diameters of the crosslinked ethylene / α-olefin copolymers (C-2C) to (C-14C).

(Preparation of crosslinked ethylene / α-olefin copolymers (C-15C) to (C-24C))
As shown in Table 9C and Table 10C, except that the type of aqueous olefin resin dispersion (B) and the amount of t-butylcumyl peroxide added were changed, the crosslinked ethylene / α-olefin copolymer (C-1C) and Similarly, crosslinked ethylene / α-olefin copolymers (C-15C) to (C-24C) were obtained. Tables 9C and 10C show the gel contents and volume average particle diameters of the crosslinked ethylene / α-olefin copolymers (C-15C) to (C-24C).

<Graft copolymer (D)>
(Preparation of graft copolymer (D-1C))
An aqueous olefin resin dispersion (B-1C) (70 parts as solid content of ethylene / propylene copolymer (A-1C)) is placed in a stainless polymerization tank equipped with a stirrer, and an aqueous olefin resin dispersion (B-1C) is added. Ion-exchanged water was added to the solution so that the solid concentration was 30%, and 0.006 part of ferrous sulfate, 0.3 part of sodium pyrophosphate and 0.35 part of fructose were added, and the temperature was set to 80 ° C. Styrene (23.4 parts), acrylonitrile (6.6 parts) and cumene hydroperoxide (0.6 parts) were continuously added for 150 minutes, and the polymerization temperature was kept at 80 ° C. to carry out emulsion polymerization. After polymerization, an antioxidant is added to the aqueous dispersion containing the graft copolymer (D-1C), solids are precipitated with sulfuric acid, and after washing, dehydration and drying, A polymer (D-1C) was obtained. The graft ratio of the graft copolymer (D-1C) was measured and found to be 30%. The results are shown in Table 11C.

(Preparation of graft copolymers (D-2C) to (D-17C))
As shown in Table 11C to Table 14C, except that the type of the aqueous olefin resin dispersion (B) was changed, in the same manner as the graft copolymer (D-1C), the graft copolymer (D-2C) to ( D-17C) was obtained. The graft ratios of the graft copolymers (D-2C) to (D-17C) are shown in Tables 11C to 14C.

(Preparation of graft copolymers (D-18C) to (D-23C), (D-25C) to (D-32C))
As shown in Tables 15C to 17C, the graft copolymer (D-1C) was used except that the aqueous olefin resin dispersion (B) was changed to an aqueous dispersion containing a crosslinked ethylene / α-olefin copolymer (C). ), Graft copolymers (D-18C) to (D-23C) and (D-25C) to (D-32C) were obtained. The graft ratios of the graft copolymers (D-18C) to (D-23C) and (D-25C) to (D-32C) are shown in Tables 15C to 17C.

(Preparation of graft copolymer (D-24C))
A stainless polymerization tank equipped with a stirrer was charged with 70 parts of ethylene / propylene copolymer (A-1C) and 300 parts of toluene, and the contents were stirred at 70 ° C. for 1 hour to uniformly dissolve. After sufficiently purging with nitrogen, 23.4 parts of styrene, 6.6 parts of acrylonitrile, 0.24 parts of t-dodecyl mercaptan and 0.22 parts of t-butylperoxyisopropyl monocarbonate were added, and the internal temperature was 110 ° C. The mixture was heated up to react for 4 hours. The internal temperature was raised to 120 ° C. and reacted for 2 hours. After the polymerization, the internal temperature was cooled to 100 ° C., and 0.2 part of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenol) -propionate was added. The reaction mixture was extracted, and unreacted substances and the solvent were distilled off by steam distillation. The volatile matter was substantially devolatilized at 220 ° C. and 93.325 kPa vacuum in a twin screw extruder with a 30 mmφ vacuum vent (“PCM30” manufactured by Ikegai Co., Ltd.), pelletized, and graft copolymer (D-15C ) The graft ratio of the graft copolymer (D-24C) was measured and found to be 26%. When the volume average particle diameter of the ethylene / α-olefin copolymer (A) in the thermoplastic resin composition was confirmed by an electron microscope, it was 0.39 μm. The results are shown in Table 16C.

(Preparation of graft copolymers (D-33C) and (D-34C))
As shown in Table 18C, the graft copolymers (D-33C) and (D-34C) were the same as the graft copolymer (D-1C) except that the type of the aqueous olefin resin dispersion (B) was changed. ) The graft ratios of the graft copolymers (D-33C) and (D-34C) are shown in Table 18C.

(Preparation of graft copolymers (D-35C) to (D-44C))
As shown in Table 18C to Table 20C, the graft copolymer (D-1C) was used except that the aqueous olefin resin dispersion (B) was changed to an aqueous dispersion containing a crosslinked ethylene / α-olefin copolymer (C). ) To obtain graft copolymers (D-35C) to (D-44C). The graft ratios of the graft copolymers (D-35C) to (D-44C) are shown in Tables 18C to 20C.

<Graft Copolymer (F)> (Preparation of Graft Copolymer (F-1C))
0.97 part of dipotassium alkenyl succinate, 175 parts of ion-exchanged water, 50 parts of n-butyl acrylate, 0.16 part of allyl methacrylate, 0.08 part of 1,3-butylene glycol dimethacrylate, and t-butyl hydroperoxide 0.1 part of the mixture was charged to the reactor. By passing a nitrogen stream through the reactor, the inside of the reactor was purged with nitrogen, and the temperature was raised to 60 ° C. When the internal temperature reached 50 ° C., an aqueous solution consisting of 0.00015 part of ferrous sulfate, 0.00045 part of ethylenediaminetetraacetic acid disodium salt, 0.24 part of Rongalite, and 5 parts of ion-exchanged water was added. Polymerization was started and the internal temperature was raised to 75 ° C. Further, this state was maintained for 1 hour to obtain an aqueous dispersion of a crosslinked acrylic ester rubber-like polymer (E-1C). The volume average particle diameter of the crosslinked acrylate rubber polymer (E-1C) dispersed in the aqueous dispersion was 0.082 μm.

While maintaining the internal temperature of the reactor at 75 ° C., Rongalite 0.15 parts, alkenyl succinate dipotassium 0.15 parts, and 50 parts (as a solid content) of a crosslinked acrylate rubber polymer (E-1C). An aqueous solution consisting of 65 parts and 10 parts of ion-exchanged water was added, and then a mixed solution consisting of 6.3 parts of acrylonitrile, 18.7 parts of styrene and 0.11 part of t-butyl hydroperoxide was added dropwise over 1 hour. And graft polymerization. Five minutes after the completion of the dropping, an aqueous solution comprising 0.001 part of ferrous sulfate, 0.003 part of ethylenediaminetetraacetic acid disodium salt, 0.15 part of Rongalite, and 5 parts of ion-exchanged water was added, and then acrylonitrile 6 A mixture of 3 parts, 18.7 parts of styrene, 0.19 parts of t-butyl hydroperoxide, and 0.014 part of n-octyl mercaptan was added dropwise over 1 hour for graft polymerization. After completion of the dropwise addition, the internal temperature was kept at 75 ° C. for 10 minutes and then cooled. When the internal temperature reached 60 ° C., 0.2 parts of antioxidant (Yantomi Pharmaceutical Co., Ltd., Antage W500) and alkenyl succinic acid were added. An aqueous solution in which 0.2 part of dipotassium acid was dissolved in 5 parts of ion-exchanged water was added. Through the above operation, graft polymerization of acrylonitrile and styrene onto the crosslinked acrylate rubber polymer (E-1C) was performed. Subsequently, the aqueous dispersion of the reaction product was coagulated with an aqueous sulfuric acid solution, washed with water, and dried to obtain a graft copolymer (F-1C).

(Preparation of graft copolymer (F-2C))
1.2 parts of dipotassium alkenyl succinate, 175 parts of ion exchange water, 50 parts of n-butyl acrylate, 0.16 part of allyl methacrylate, 0.08 part of 1,3-butylene glycol dimethacrylate, and t-butyl hydroperoxide 0.1 part of the mixture was charged to the reactor. By passing a nitrogen stream through the reactor, the inside of the reactor was purged with nitrogen, and the temperature was raised to 60 ° C. When the internal temperature reached 50 ° C., an aqueous solution consisting of 0.00015 part of ferrous sulfate, 0.00045 part of ethylenediaminetetraacetic acid disodium salt, 0.24 part of Rongalite, and 5 parts of ion-exchanged water was added. Polymerization was started and the internal temperature was raised to 75 ° C. Furthermore, this state was maintained for 1 hour to obtain an aqueous dispersion of a cross-linked acrylic acid ester rubbery polymer (E-2C). The volume average particle diameter of the crosslinked acrylic ester rubber-like polymer (E-2C) dispersed in the aqueous dispersion was 0.037 μm.

While maintaining the internal temperature of the reactor at 75 ° C., Rongalite 0.15 parts, alkenyl succinate dipotassium 0.15 parts with respect to 50 parts (as a solid content) of the crosslinked acrylate rubber polymer (E-2C). An aqueous solution consisting of 65 parts and 10 parts of ion-exchanged water was added, and then a mixed solution consisting of 6.3 parts of acrylonitrile, 18.7 parts of styrene and 0.11 part of t-butyl hydroperoxide was added dropwise over 1 hour. And graft polymerization. Five minutes after the completion of the dropping, an aqueous solution comprising 0.001 part of ferrous sulfate, 0.003 part of ethylenediaminetetraacetic acid disodium salt, 0.15 part of Rongalite, and 5 parts of ion-exchanged water was added, and then acrylonitrile 6 A mixture of 3 parts, 18.7 parts of styrene, 0.19 parts of t-butyl hydroperoxide, and 0.014 part of n-octyl mercaptan was added dropwise over 1 hour for graft polymerization. After completion of the dropwise addition, the internal temperature was kept at 75 ° C. for 10 minutes and then cooled. When the internal temperature reached 60 ° C., 0.2 parts of antioxidant (Yantomi Pharmaceutical Co., Ltd., Antage W500) and alkenyl succinic acid were added. An aqueous solution in which 0.2 part of dipotassium acid was dissolved in 5 parts of ion-exchanged water was added. By the above operation, graft polymerization of acrylonitrile and styrene onto the crosslinked acrylic ester rubber polymer (E-2C) was performed. Subsequently, the aqueous dispersion of the reaction product was coagulated with an aqueous sulfuric acid solution, washed with water, and dried to obtain a graft copolymer (F-2C).

(Preparation of graft copolymer (F-3C))
1.08 parts dipotassium alkenyl succinate, 175 parts ion-exchanged water, 50 parts n-butyl acrylate, 0.16 parts allyl methacrylate, 0.08 parts 1,3-butylene glycol dimethacrylate, and t-butyl hydroperoxide 0.1 part of the mixture was charged to the reactor. By passing a nitrogen stream through the reactor, the inside of the reactor was purged with nitrogen, and the temperature was raised to 60 ° C. When the internal temperature reached 50 ° C., an aqueous solution consisting of 0.00015 part of ferrous sulfate, 0.00045 part of ethylenediaminetetraacetic acid disodium salt, 0.24 part of Rongalite, and 5 parts of ion-exchanged water was added. Polymerization was started and the internal temperature was raised to 75 ° C. Further, this state was maintained for 1 hour to obtain an aqueous dispersion of a cross-linked acrylic ester rubbery polymer (E-3C). The volume average particle diameter of the crosslinked acrylate rubber polymer (E-3C) dispersed in the aqueous dispersion was 0.050 μm.

While maintaining the internal temperature of the reactor at 75 ° C., Rongalite 0.15 parts, alkenyl succinate dipotassium 0.15 parts with respect to 50 parts (as a solid content) of a crosslinked acrylate rubber polymer (E-3C). An aqueous solution consisting of 65 parts and 10 parts of ion-exchanged water was added, and then a mixed solution consisting of 6.3 parts of acrylonitrile, 18.7 parts of styrene and 0.11 part of t-butyl hydroperoxide was added dropwise over 1 hour. And graft polymerization. Five minutes after the completion of the dropping, an aqueous solution comprising 0.001 part of ferrous sulfate, 0.003 part of ethylenediaminetetraacetic acid disodium salt, 0.15 part of Rongalite, and 5 parts of ion-exchanged water was added, and then acrylonitrile 6 A mixture of 3 parts, 18.7 parts of styrene, 0.19 parts of t-butyl hydroperoxide, and 0.014 part of n-octyl mercaptan was added dropwise over 1 hour for graft polymerization. After completion of the dropwise addition, the internal temperature was kept at 75 ° C. for 10 minutes and then cooled. When the internal temperature reached 60 ° C., 0.2 parts of antioxidant (Yantomi Pharmaceutical Co., Ltd., Antage W500) and alkenyl succinic acid were added. An aqueous solution in which 0.2 part of dipotassium acid was dissolved in 5 parts of ion-exchanged water was added. Through the above operation, graft polymerization of acrylonitrile and styrene onto the crosslinked acrylic acid ester rubbery polymer (E-3C) was performed. Subsequently, the aqueous dispersion of the reaction product was coagulated with an aqueous sulfuric acid solution, washed with water, and dried to obtain a graft copolymer (F-3C).

(Preparation of graft copolymer (F-4C))
0.59 parts dipotassium alkenyl succinate, 175 parts ion-exchanged water, 50 parts n-butyl acrylate, 0.16 parts allyl methacrylate, 0.08 parts 1,3-butylene glycol dimethacrylate, and t-butyl hydroperoxide 0.1 part of the mixture was charged to the reactor. By passing a nitrogen stream through the reactor, the inside of the reactor was purged with nitrogen, and the temperature was raised to 60 ° C. When the internal temperature reached 50 ° C., an aqueous solution consisting of 0.00015 part of ferrous sulfate, 0.00045 part of ethylenediaminetetraacetic acid disodium salt, 0.24 part of Rongalite, and 5 parts of ion-exchanged water was added. Polymerization was started and the internal temperature was raised to 75 ° C. Furthermore, this state was maintained for 1 hour to obtain an aqueous dispersion of a cross-linked acrylic acid ester rubbery polymer (E-4C). The volume average particle diameter of the crosslinked acrylate rubber polymer (E-4C) dispersed in the aqueous dispersion was 0.18 μm.

While maintaining the internal temperature of the reactor at 75 ° C., Rongalite 0.15 parts, alkenyl succinate dipotassium 0.15 parts, and 50 parts of crosslinked acrylic ester rubber polymer (E-4C) (as a solid content). An aqueous solution consisting of 65 parts and 10 parts of ion-exchanged water was added, and then a mixed solution consisting of 6.3 parts of acrylonitrile, 18.7 parts of styrene and 0.11 part of t-butyl hydroperoxide was added dropwise over 1 hour. And graft polymerization. Five minutes after the completion of the dropping, an aqueous solution comprising 0.001 part of ferrous sulfate, 0.003 part of ethylenediaminetetraacetic acid disodium salt, 0.15 part of Rongalite, and 5 parts of ion-exchanged water was added, and then acrylonitrile 6 A mixture of 3 parts, 18.7 parts of styrene, 0.19 parts of t-butyl hydroperoxide, and 0.014 part of n-octyl mercaptan was added dropwise over 1 hour for graft polymerization. After completion of the dropwise addition, the internal temperature was kept at 75 ° C. for 10 minutes and then cooled. When the internal temperature reached 60 ° C., 0.2 parts of antioxidant (Yantomi Pharmaceutical Co., Ltd., Antage W500) and alkenyl succinic acid were added. An aqueous solution in which 0.2 part of dipotassium acid was dissolved in 5 parts of ion-exchanged water was added. Through the above operation, graft polymerization of acrylonitrile and styrene onto the crosslinked acrylate rubber polymer (E-4C) was performed. Subsequently, the aqueous dispersion of the reaction product was coagulated with an aqueous sulfuric acid solution, washed with water, and dried to obtain a graft copolymer (F-4C).

(Preparation of graft copolymer (F-5C))
0.43 part of dipotassium alkenyl succinate, 175 parts of ion exchange water, 50 parts of n-butyl acrylate, 0.16 part of allyl methacrylate, 0.08 part of 1,3-butylene glycol dimethacrylate, and t-butyl hydroperoxide 0.1 part of the mixture was charged to the reactor. By passing a nitrogen stream through the reactor, the inside of the reactor was purged with nitrogen, and the temperature was raised to 60 ° C. When the internal temperature reached 50 ° C., an aqueous solution consisting of 0.00015 part of ferrous sulfate, 0.00045 part of ethylenediaminetetraacetic acid disodium salt, 0.24 part of Rongalite, and 5 parts of ion-exchanged water was added. Polymerization was started and the internal temperature was raised to 75 ° C. Further, this state was maintained for 1 hour to obtain an aqueous dispersion of a crosslinked acrylic ester rubber-like polymer (E-5C). The volume average particle diameter of the crosslinked acrylic ester rubber-like polymer (E-5C) dispersed in the aqueous dispersion was 0.24 μm.

While maintaining the internal temperature of the reactor at 75 ° C., Rongalite 0.15 parts, alkenyl succinate dipotassium 0.15 parts with respect to 50 parts (as a solid content) of a crosslinked acrylate rubber polymer (E-5C). An aqueous solution consisting of 65 parts and 10 parts of ion-exchanged water was added, and then a mixed solution consisting of 6.3 parts of acrylonitrile, 18.7 parts of styrene and 0.11 part of t-butyl hydroperoxide was added dropwise over 1 hour. And graft polymerization. Five minutes after the completion of the dropping, an aqueous solution comprising 0.001 part of ferrous sulfate, 0.003 part of ethylenediaminetetraacetic acid disodium salt, 0.15 part of Rongalite, and 5 parts of ion-exchanged water was added, and then acrylonitrile 6 A mixture of 3 parts, 18.7 parts of styrene, 0.19 parts of t-butyl hydroperoxide, and 0.014 part of n-octyl mercaptan was added dropwise over 1 hour for graft polymerization. After completion of the dropwise addition, the internal temperature was kept at 75 ° C. for 10 minutes and then cooled. When the internal temperature reached 60 ° C., 0.2 parts of antioxidant (Yantomi Pharmaceutical Co., Ltd., Antage W500) and alkenyl An aqueous solution in which 0.2 part of dipotassium acid was dissolved in 5 parts of ion-exchanged water was added. Through the above operation, graft polymerization of acrylonitrile and styrene onto the crosslinked acrylate rubber polymer (E-5C) was performed. Subsequently, the aqueous dispersion of the reaction product was coagulated with an aqueous sulfuric acid solution, washed with water, and dried to obtain a graft copolymer (F-5C).

<Methacrylate ester resin (G)>
(Preparation of methacrylate ester resin (G-1C))
In a stainless steel polymerization tank equipped with a stirrer, 150 parts of ion exchange water, 99 parts of methyl methacrylate, 1 part of methyl acrylate, 0.2 part of 2,2′-azobis (isobutyronitrile), 0.25 part of n-octyl mercaptan , 0.47 part of calcium hydroxyapatite and 0.003 part of potassium alkenyl succinate were charged. The internal temperature of the polymerization tank was set to 75 ° C. for 3 hours, and the temperature was raised to 90 ° C. for 1 hour. The contents were extracted, washed with a centrifugal dehydrator, and dried to obtain a powdery methacrylate resin (G-1C). The monomers are shown in Table 21C.

(Preparation of methacrylate ester resin (G-2C))
In a stainless polymerization tank equipped with a stirrer, 150 parts of ion exchange water, 82 parts of methyl methacrylate, 12 parts of N-phenylmaleimide, 6 parts of styrene, 0.2 part of 2,2′-azobis (isobutyronitrile), n-octyl Mercaptan (0.25 part) and polyvinyl alcohol (0.7 part) were charged. The internal temperature of the polymerization tank was set at 75 ° C. for 3 hours, and the temperature was raised to 90 ° C. for 1 hour. The contents were extracted, washed with a centrifugal dehydrator, and dried to obtain a powdery methacrylate resin (G-2C). The monomers are shown in Table 21C.

(Preparation of Methacrylate Resin (G-3C) to (G-11C))
As shown in Table 21C and Table 22C, except that the type of the vinyl monomer mixture (m3) was changed, in the same manner as the methacrylate ester resin (G-2C), the methacrylate ester resin (G-3C) to (G-11C) was obtained.

<Styrene copolymer (H)>
(Preparation of styrene copolymer (H-1C))
In a stainless steel polymerization tank equipped with a stirrer substituted with nitrogen, 120 parts of ion exchange water, 0.1 part of polyvinyl alcohol, 0.3 part of 2,2′-azobis (isobutyronitrile), 25 parts of acrylonitrile, 75 parts of styrene, t -0.35 part of dodecyl mercaptan was charged and reacted at an initial temperature of 60 ° C for 5 hours. The temperature was raised to 120 ° C. and reacted for 4 hours. The contents were taken out to obtain a styrene copolymer (H-1C).

(Preparation of styrene copolymer (H-2C))
In a stainless steel polymerization tank equipped with a stirrer, 150 parts of ion exchange water, 7 parts of methyl methacrylate, 23 parts of acrylonitrile, 70 parts of styrene, 0.2 part of 2,2′-azobis (isobutyronitrile), n-octyl mercaptan 0 .25 parts, calcium hydroxyapatite 0.47 part, and potassium alkenyl succinate 0.003 part were charged, the internal temperature was raised to 75 ° C., and the reaction was performed for 3 hours. The reaction was completed by raising the temperature to 90 ° C. and holding for 60 minutes. The contents were taken out, repeatedly washed with a centrifugal dehydrator, dehydrated, and dried to obtain a styrene copolymer (H-2C).

(Preparation of styrenic copolymers (H-3C) to (H-5C))
As shown in Table 23C, except that the amount of the vinyl monomer mixture (m4) was changed, the styrene copolymer (H-3C) ˜ ( H-5C) was obtained.

[Example 1C]
10 parts of graft copolymer (D-1C), 14 parts of graft copolymer (F-1C) and 76 parts of methacrylic ester resin (G-1C) were mixed and a twin screw extruder with a 30 mmφ vacuum vent (Ikekai A thermoplastic resin composition was prepared by melt-kneading at 240 ° C. and 93.325 kPa vacuum using a “PCM30” manufactured by the company. The MVR of the thermoplastic resin composition is shown in Table 15C.
The thermoplastic resin composition was pelletized and various molded products were molded, and impact resistance, color development, scratch resistance, scratch resistance, and heat resistance were evaluated. The results are shown in Table 24C.

[Examples 2C to 72C]
A thermoplastic resin composition was prepared and MVR was measured in the same manner as in Example 1C, except that the formulation shown in Tables 24C to 32C was changed.
The thermoplastic resin composition was pelletized and various molded products were molded, and impact resistance, color development, scratch resistance, scratch resistance, and heat resistance were evaluated. The results are shown in Tables 24C to 32C.

[Comparative Examples 1C to 17C]
A thermoplastic resin composition was prepared and MVR was measured in the same manner as in Example 1C, except that the formulation shown in Table 33C to Table 35C was changed.
The thermoplastic resin composition was pelletized and various molded products were molded, and impact resistance, color development, scratch resistance, scratch resistance, and heat resistance were evaluated. The results are shown in Table 33C to Table 35C.

The thermoplastic resin compositions of Examples 1C to 72C were excellent in fluidity. In addition, the molded products obtained in Examples 1C to 72C were excellent in impact resistance, heat resistance, color development, scratch resistance, and scratch resistance.
Therefore, the thermoplastic resin composition according to the fourth aspect of the present invention has excellent fluidity, and when the thermoplastic resin composition according to the fourth aspect of the present invention is used, impact resistance, color developability, and scratch resistance are improved. It can be seen that a molded article having excellent scratch resistance and scratch resistance can be obtained and can be applied to uses such as vehicle interior parts, vehicle exterior parts, office equipment, home appliances, and building materials.

On the other hand, from the results of Comparative Examples 1C to 17C, those other than the present invention had low impact resistance and scratch resistance of the molded product.

<Measurement method 3 of volume average particle diameter>
The volume average particle diameter (MV) was measured using a microtrack (“Nanotrack 150” manufactured by Nikkiso Co., Ltd.) using pure water as a measurement solvent.
The ethylene / α-olefin copolymer (A) dispersed in the aqueous olefin resin dispersion (B), the crosslinked ethylene / α-olefin copolymer (C) dispersed in the aqueous dispersion, The volume average particle diameter of the composite rubber-like polymer (L) dispersed in the aqueous dispersion is the same as that of the ethylene / α-olefin copolymer (A) or the crosslinked ethylene / α-olefin copolymer in the thermoplastic resin composition. It has been confirmed by image analysis with an electron microscope that the volume average particle diameter of the polymer (C) and the composite rubber-like polymer (L) is shown.

<Melting and kneading 5>
Graft copolymer (D), graft copolymer (M), methacrylic ester resin (G), and other components as necessary are mixed in the formulations shown in Tables 24D to 35D, and a vacuum vent with 30 mmφ 2 A thermoplastic resin composition was obtained by melt kneading in a shaft extruder (“PCM30” manufactured by Ikegai Co., Ltd.) at a cylinder temperature of 200 to 260 ° C. and a vacuum of 93.325 kPa. Moreover, after melt-kneading as needed, pelletization was performed using a pelletizer (“SH type pelletizer” manufactured by Souken Co., Ltd.).

<Injection molding 5>
The pellets of the thermoplastic resin composition obtained by melt kneading are subjected to Charpy impact using an injection molding machine (“IS55FP-1.5A” manufactured by Toshiba Machine Co., Ltd.) at a cylinder temperature of 200 to 260 ° C. and a mold temperature of 60 ° C. A test specimen for test, a 2 mm-thick flat plate (10 cm × 10 cm) was obtained. Further, a test piece for evaluating the lubricity was obtained with an injection molding machine (“SG150-SYCAPM IV” manufactured by Sumitomo Heavy Industries, Ltd.) under conditions of a cylinder temperature of 200 to 260 ° C. and a mold temperature of 60 ° C.

<Evaluation of lubricity: before degreasing>
Using the test piece 21 having the rib structure 21a shown in FIG. 2 and the test piece 22 having a flat portion, it was investigated whether or not a squeak noise was generated when reciprocating while applying a load of 500 g or 1 kg. Evaluated by criteria. Δ or more was considered to have lubricity.
(Double-circle): A squeak noise does not generate | occur | produce in any of load 500g and 1kg.
○: A small squeak noise is generated when the load is 1 kg, but not when the load is 500 g.
Δ: A small squeak noise is produced at both loads of 500 g and 1 kg.
X: A squeak noise is generated at any load of 500 g and 1 kg.

<Evaluation of lubricity: after degreasing>
The specimen 21 having the rib structure 21a shown in FIG. 2 and the specimen 22 having a flat surface portion are annealed at 60 ° C. for 10 days, and then the surfaces of the specimen 21 and the specimen 22 are degreased with isopropyl alcohol to cause bleeding components. Removed. Generation | occurrence | production of the squeak noise after degreasing was investigated like the said method, and the following reference | standard evaluated. △ or more is regarded as having a permanent lubricity.
(Double-circle): A squeak noise does not generate | occur | produce in any of load 500g and 1kg.
○: A small squeak noise is generated when the load is 1 kg, but not when the load is 500 g.
Δ: A small squeak noise is produced at both loads of 500 g and 1 kg.
X: A squeak noise is generated at any load of 500 g and 1 kg.

<Each component>
In the following examples, the following ethylene / α-olefin copolymer (A), olefin resin aqueous dispersion (B), crosslinked ethylene / α-olefin copolymer (C), graft copolymer (D), Organosiloxane (La), composite rubber-like polymer (L), graft copolymer (M), methacrylic ester resin (G), and styrene copolymer (H) were used.

<Ethylene / α-olefin copolymer (A)>
(Preparation of ethylene / propylene copolymer (A-1D))
After fully substituting the stainless polymerization tank equipped with a 20 L stirrer with nitrogen, 10 L of dehydrated and purified hexane was added, and ethylaluminum sesquichloride (Al (C ₂ H ₅ ) _1.5 · Cl ₁ prepared to 8.0 mmol / L was added. ₅ ) was continuously supplied at a rate of 5 L / h for 1 hour, and then a hexane solution of VO (OC ₂ H ₅ ) Cl ₂ adjusted to 0.8 mmol / L as a catalyst was further added to 5 L / h. Hexane was continuously fed in an amount of 5 L / h. On the other hand, from the upper part of the polymerization tank, the polymerization liquid was continuously extracted so that the polymerization liquid in the polymerization tank was always 10 L. Using a bubbling tube, ethylene was supplied in an amount of 2000 L / h, propylene was supplied in an amount of 1000 L / h, hydrogen was supplied in an amount of 8 L / h, and a polymerization reaction was performed at 35 ° C.
A polymerization reaction was performed under the above conditions to obtain a polymerization solution containing an ethylene / propylene copolymer (A-1D). The obtained polymerization solution was deashed with hydrochloric acid, poured into methanol for precipitation, and then dried to obtain an ethylene / propylene copolymer (A-1D). The properties of the ethylene / propylene copolymer (A-1D) polymer are shown in Table 1D.

(Preparation of ethylene / propylene copolymers (A-2D) to (A-5D))
The ethylene / propylene copolymers (A-2D) to (A-5D) were prepared in the same manner as the ethylene / propylene copolymer (A-1D) except that the hydrogen supply amount was changed as shown in Table 1D. Obtained. Table 1D shows the properties of the ethylene / propylene copolymers (A-2D) to (A-5D).

(Preparation of ethylene / propylene copolymer (A-6D))
After sufficiently substituting a 20 L stainless steel tank with a stirrer with nitrogen, 10 L of dehydrated and purified hexane was added, and 110 L of propylene (standard state) and 800 mL of hydrogen were added. After heating to 40 ° C., it was pressurized with ethylene so that the total pressure was 0.6 MPa [gage].
When the internal pressure reached 0.6 MPa [gage], 10 mL of a 1.0 mM / mL hexane solution of triisobutylaluminum (TIBA) was injected with nitrogen. Triphenylcarbenium (tetrakispentafluorophenyl) borate prepared in advance was 0.16 mM in terms of boron, and [dimethyl (t-butylamide) (tetramethyl-η5-cyclopentadienyl) silane] titanium chloride was changed to 0. Polymerization was initiated by injecting 30 mL of a toluene solution containing 0004 mM with nitrogen. Thereafter, the temperature was adjusted to 40 ° C. for 5 minutes, and ethylene was supplied so that the pressure became 0.6 MPa [gage]. Five minutes after the start of the polymerization, 50 mL of methanol was inserted to terminate the polymerization, and the pressure was released to atmospheric pressure to obtain a polymerization solution containing an ethylene / propylene copolymer (A-6D). The obtained polymerization solution was deashed with hydrochloric acid, poured into methanol for precipitation, and then dried to obtain an ethylene / propylene copolymer (A-6D). Table 2D shows the properties of the ethylene / propylene copolymer (A-6D) polymer.

(Preparation of ethylene / propylene copolymer (A-7D))
20 parts of ethylene / propylene copolymer (A-1D) and 80 parts of ethylene / propylene copolymer (A-6D) are mixed and a twin screw extruder with a 30 mmφ vacuum vent (“PCM30” manufactured by Ikegai Co., Ltd.) The mixture was melt-kneaded at 200 ° C. and 93.325 kPa vacuum to prepare an ethylene / propylene copolymer (A-7D). Properties of the ethylene / propylene copolymer (A-7D) polymer are shown in Table 2D.

(Preparation of ethylene / propylene copolymer (A-11D))
An ethylene / propylene copolymer (A-11D) is obtained in the same manner as the ethylene / propylene copolymer (A-1D) except that VCl ₄ is used instead of VO (OC ₂ H ₅ ) Cl ₂ as a catalyst. It was. Table 1D shows the properties of the ethylene / propylene copolymer (A-11D).

(Preparation of ethylene / propylene copolymer (A-8D))
Mixing 75 parts of ethylene / propylene copolymer (A-1D) and 25 parts of ethylene / propylene copolymer (A-11D), twin screw extruder with 30 mmφ vacuum vent (Ikegai, “PCM30”) And kneaded at 200 ° C. and 93.325 kPa vacuum to prepare an ethylene / propylene copolymer (A-8D). Table 2D shows the properties of the ethylene / propylene copolymer (A-8D).

(Preparation of ethylene / propylene copolymer (A-9D))
Mixing 50 parts of ethylene / propylene copolymer (A-1D) and 50 parts of ethylene / propylene copolymer (A-11D), a twin screw extruder equipped with a 30 mmφ vacuum vent (“PCM30” manufactured by Ikegai Co., Ltd.) And kneaded at 200 ° C. and 93.325 kPa vacuum to prepare an ethylene / propylene copolymer (A-9D). Table 2D shows the properties of the ethylene / propylene copolymer (A-9D) polymer.

(Preparation of ethylene / propylene copolymer (A-10D))
20 parts of ethylene / propylene copolymer (A-1D) and 80 parts of ethylene / propylene copolymer (A-11D) are mixed and a twin screw extruder with a 30 mmφ vacuum vent (“Ikegai Co., Ltd.,“ PCM30 ”) The mixture was melt-kneaded at 200 ° C. and 93.325 kPa vacuum to prepare an ethylene / propylene copolymer (A-10D). Table 2D shows the properties of the ethylene / propylene copolymer (A-10D) polymer.

(Preparation of ethylene / propylene copolymer (A-12D), (A-13D))
The ethylene / propylene copolymers (A-12D) and (A-13D) were prepared in the same manner as the ethylene / propylene copolymer (A-1D) except that the hydrogen supply amount was changed as shown in Table 3D. Obtained. Table 3D shows the properties of the ethylene / propylene copolymers (A-12D) and (A-13D).

<Olefin resin aqueous dispersion (B)>
(Preparation of aqueous dispersion of olefin resin (B-1D))
100 parts of ethylene / propylene copolymer (A-1D) and maleic anhydride-modified polyethylene (“Mitsui Chemicals,“ Mitsui High Wax 2203A ”) as the acid-modified olefin polymer, mass average molecular weight: 2,700, acid value: 30 mg / g) 20 parts and 5 parts of potassium oleate as an anionic emulsifier were mixed.
This mixture is supplied at 4 kg / h from a hopper of a twin screw extruder (Ikegai, “PCM30”, L / D = 40), and water is supplied from a supply port provided in a vent portion of the twin screw extruder. While continuously supplying an aqueous solution obtained by mixing 0.5 part of potassium oxide and 2.4 parts of ion-exchanged water, it was heated to 220 ° C., melt-kneaded and extruded. The melt-kneaded product was continuously supplied to a cooling device attached to the tip of the twin screw extruder and cooled to 90 ° C. Then, the solid discharged from the tip of the twin screw extruder is poured into warm water at 80 ° C., continuously dispersed, diluted to a solid content concentration of about 40% by mass, and an aqueous olefin resin dispersion (B -1D) was obtained.
Table 4D shows the volume average particle size of the ethylene / α-olefin copolymer (A) dispersed in the aqueous olefin resin dispersion (B-1D).

(Preparation of aqueous olefin resin dispersions (B-2D) to (B-11D))
As shown in Table 4D and Table 5D, the same procedure as in the aqueous olefin resin dispersion (B-1D) was conducted except that (A-1D) was changed from (A-2D) to (A-11D) as the component A. Thus, aqueous olefin resin dispersions (B-2D) to (B-11D) were obtained.
Tables 4D and 5D show the volume average particle diameters of the ethylene / α-olefin copolymers (A) dispersed in each of the aqueous olefin resin dispersions (B-2D) to (B-11D).

(Preparation of aqueous olefin resin dispersions (B-12D) to (B-17D))
As shown in Table 5D, the aqueous olefin resin dispersion was the same as the aqueous olefin resin dispersion (B-1D) except that the number of added parts of potassium hydroxide and the number of added parts of ion exchange water during emulsification were changed. (B-12D) to (B-17D) were obtained.
Table 5D shows the volume average particle diameter of the ethylene / α-olefin copolymer (A) dispersed in each of the aqueous olefin resin dispersions (B-12D) to (B-17D).

(Preparation of aqueous dispersion of olefin resin (B-18D), (B-19D))
As shown in Table 6D, the olefin resin was the same as the aqueous olefin resin dispersion (B-1D) except that (A-1D) was changed to (A-12D) and (A-13D) as the A component. Aqueous dispersions (B-18D) and (B-19D) were obtained.
Table 6D shows the volume average particle size of the ethylene / α-olefin copolymer (A) dispersed in each of the aqueous dispersions of olefin resin (B-18D) and (B-19D).

<Crosslinked ethylene / α-olefin copolymer (C)>
(Preparation of cross-linked ethylene / α-olefin copolymer (C-1D))
Ion exchange water was added to the olefin resin aqueous dispersion (B-1D) (100 parts as a solid content) so that the solid content concentration was 35%, and 0.5 parts of t-butylcumyl peroxide as an organic peroxide, As a polyfunctional compound, 1 part of divinylbenzene was added and reacted at 130 ° C. for 5 hours to prepare a crosslinked ethylene / α-olefin copolymer (C-1). Table 7D shows the gel content and volume average particle size of the crosslinked ethylene / α-olefin copolymer (C-1D).

(Preparation of crosslinked ethylene / α-olefin copolymers (C-2D) to (C-14D))
As shown in Table 7D and Table 8D, the cross-linked ethylene / α-olefin copolymer (C-1D) and the olefin resin aqueous dispersion (B) and the addition amount of t-butylcumyl peroxide were changed except that Similarly, crosslinked ethylene / α-olefin copolymers (C-2D) to (C-14D) were obtained. Tables 7D and 8D show the gel contents and volume average particle diameters of the crosslinked ethylene / α-olefin copolymers (C-2D) to (C-14D).

(Preparation of crosslinked ethylene / α-olefin copolymers (C-15D) to (C-24D))
As shown in Table 9D and Table 10D, except that the type of olefin resin aqueous dispersion (B) and the amount of t-butylcumyl peroxide added were changed, the crosslinked ethylene / α-olefin copolymer (C-1D) and Similarly, crosslinked ethylene / α-olefin copolymers (C-15D) to (C-24D) were obtained. Tables 9D and 10D show the gel contents and volume average particle diameters of the crosslinked ethylene / α-olefin copolymers (C-15D) to (C-24D).

<Graft copolymer (D)>
(Preparation of graft copolymer (D-1D))
An aqueous olefin resin dispersion (B-1D) (70 parts as solid content of ethylene / propylene copolymer (A-1D)) is placed in a stainless polymerization tank equipped with a stirrer, and the aqueous olefin resin dispersion (B-1D) is added. Ion-exchanged water was added to the solution so that the solid concentration was 30%, and 0.006 part of ferrous sulfate, 0.3 part of sodium pyrophosphate and 0.35 part of fructose were added, and the temperature was set to 80 ° C. Styrene (23.4 parts), acrylonitrile (6.6 parts) and cumene hydroperoxide (0.6 parts) were continuously added for 150 minutes, and the polymerization temperature was kept at 80 ° C. to carry out emulsion polymerization. After the polymerization, an antioxidant is added to the aqueous dispersion containing the graft copolymer (D-1D), the solid content is precipitated with sulfuric acid, and after washing, dehydration and drying, A polymer (D-1D) was obtained. The graft ratio of the graft copolymer (D-1D) was measured and found to be 30%. The results are shown in Table 11D.

(Preparation of graft copolymers (D-2D) to (D-1D))
As shown in Table 11D to Table 14D, except that the type of the aqueous olefin resin dispersion (B) was changed, the same manner as the graft copolymer (D-1D), the graft copolymer (D-2D) to ( D-17D) was obtained. The graft ratios of the graft copolymers (D-2D) to (D-17D) are shown in Tables 11D to 14D.

(Preparation of graft copolymers (D-18D) to (D-23D), (D-25D) to (D-32D))
As shown in Tables 15D to 17D, the graft copolymer (D-1D) was used except that the aqueous olefin resin dispersion (B) was changed to an aqueous dispersion containing a crosslinked ethylene / α-olefin copolymer (C). ), Graft copolymers (D-18D) to (D-23D) and (D-25D) to (D-32D) were obtained. The graft ratios of the graft copolymers (D-18D) to (D-23D) and (D-25D) to (D-32D) are shown in Tables 15D to 17D.

(Preparation of graft copolymer (D-24D))
A stainless polymerization tank equipped with a stirrer was charged with 70 parts of ethylene / propylene copolymer (A-1D) and 300 parts of toluene, and the contents were stirred at 70 ° C. for 1 hour to uniformly dissolve. After sufficiently purging with nitrogen, 23.4 parts of styrene, 6.6 parts of acrylonitrile, 0.24 parts of t-dodecyl mercaptan and 0.22 parts of t-butylperoxyisopropyl monocarbonate were added, and the internal temperature was 110 ° C. The mixture was heated up to react for 4 hours. The internal temperature was raised to 120 ° C. and reacted for 2 hours. After the polymerization, the internal temperature was cooled to 100 ° C., and 0.2 part of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenol) -propionate was added. The reaction mixture was extracted, and unreacted substances and the solvent were distilled off by steam distillation. The volatile matter was substantially devolatilized at 220 ° C. and 93.325 kPa vacuum in a twin screw extruder with a 30 mmφ vacuum vent (“PCM30” manufactured by Ikegai Co., Ltd.), pelletized, and graft copolymer (D-15D ) The graft ratio of the graft copolymer (D-24D) was measured and found to be 26%. When the volume average particle diameter of the ethylene / α-olefin copolymer (A) in the thermoplastic resin composition was confirmed by an electron microscope, it was 0.39 μm. The results are shown in Table 16D.

(Preparation of graft copolymer (D-33D), (D-34D))
As shown in Table 18D, the graft copolymers (D-33D), (D-34D) were the same as the graft copolymers (D-1D) except that the type of the aqueous olefin resin dispersion (B) was changed. ) The graft ratios of the graft copolymers (D-33D) and (D-34D) are shown in Table 18D.

(Preparation of graft copolymers (D-35D) to (D-44D))
As shown in Tables 18D to 20D, the graft copolymer (D-1D) was used except that the aqueous olefin resin dispersion (B) was changed to an aqueous dispersion containing a crosslinked ethylene / α-olefin copolymer (C). ) To obtain graft copolymers (D-35D) to (D-44D). The graft ratios of the graft copolymers (D-35D) to (D-44D) are shown in Tables 18D to 20D.

<Graft copolymer (M)>
(Preparation of polyorganosiloxane (La-1D))
96 parts of octamethyltetracyclosiloxane, 2 parts of γ-methacryloxypropyldimethoxymethylsilane and 2 parts of ethyl orthosilicate were mixed to obtain 100 parts of a siloxane mixture. To this was added 300 parts of ion-exchanged water in which 0.67 parts of sodium dodecylbenzenesulfonate was dissolved, and the mixture was stirred at 10000 rpm for 2 minutes with a homomixer. An aqueous organosiloxane dispersion was obtained.
2 parts of dodecylbenzenesulfonic acid and 98 parts of ion-exchanged water were injected into a reactor equipped with a reagent injection container, a cooling tube, a jacket heater and a stirrer to prepare a 2% aqueous solution of dodecylbenzenesulfonic acid. With this aqueous solution heated to 85 ° C., the premixed organosiloxane aqueous dispersion was added dropwise over 4 hours, and the temperature was maintained for 1 hour after the completion of the addition, followed by cooling. The reaction solution was allowed to stand at room temperature for 48 hours and then neutralized with an aqueous sodium hydroxide solution to obtain an aqueous dispersion of polyorganosiloxane (La-1D). A part of the polyorganosiloxane (La-1D) aqueous dispersion was dried at 170 ° C. for 30 minutes to obtain a solid content concentration of 17.3%. The volume average particle diameter of polyorganosiloxane (La-1D) dispersed in the aqueous dispersion was 0.05 μm.

(Preparation of polyorganosiloxane (La-2D))
96 parts of octamethyltetracyclosiloxane, 2 parts of γ-methacryloxypropyldimethoxymethylsilane and 2 parts of ethyl orthosilicate were mixed to obtain 100 parts of a siloxane mixture. To this was added 300 parts of ion-exchanged water in which 10 parts of sodium dodecylbenzenesulfonate was dissolved, and the mixture was stirred at 10000 rpm for 2 minutes with a homomixer. An aqueous dispersion was obtained.
2 parts of dodecylbenzenesulfonic acid and 98 parts of ion-exchanged water were injected into a reactor equipped with a reagent injection container, a cooling tube, a jacket heater and a stirrer to prepare a 2% aqueous solution of dodecylbenzenesulfonic acid. With this aqueous solution heated to 85 ° C., the premixed organosiloxane aqueous dispersion was added dropwise over 4 hours, and the temperature was maintained for 1 hour after the completion of the addition, followed by cooling. The reaction solution was allowed to stand at room temperature for 48 hours and then neutralized with an aqueous sodium hydroxide solution to obtain an aqueous dispersion of polyorganosiloxane (La-2D). A part of the aqueous polyorganosiloxane (La-2D) dispersion was dried at 170 ° C. for 30 minutes and the solid content concentration was determined to be 17.3%. The volume average particle diameter of the polyorganosiloxane (La-2D) dispersed in the aqueous dispersion was 0.03 μm.

(Preparation of graft copolymer (M-1D))
In a reactor equipped with a reagent injection container, a condenser, a jacket heater and a stirrer, 119.5 parts of an aqueous dispersion of polyorganosiloxane (La-1D) and 0.8 parts of sodium polyoxyethylene alkylphenyl ether sulfate Was added, and 203 parts of ion-exchanged water was added and mixed. Thereafter, a mixture consisting of 53.2 parts of n-butyl acrylate, 0.21 part of allyl methacrylate, 0.11 part of 1,3-butylene glycol dimethacrylate and 0.13 part of t-butyl hydroperoxide was added. The atmosphere was purged with nitrogen by passing a nitrogen stream through the reactor, and the temperature was raised to 60 ° C. When the temperature inside the reactor reached 60 ° C., 0.0001 part of ferrous sulfate, 0.0003 part of ethylenediaminetetraacetic acid disodium salt and 0.24 part of Rongalite were dissolved in 10 parts of ion-exchanged water. An aqueous solution was added to initiate radical polymerization. The liquid temperature rose to 78 ° C. by polymerization of the (meth) acrylic acid ester component. This state was maintained for 1 hour, and the polymerization of the (meth) acrylic acid ester component was completed to obtain an aqueous dispersion of a composite rubber-like polymer (L1-1D). The volume average particle diameter of the composite rubber-like polymer (L1-1D) dispersed in the aqueous dispersion was 0.082 μm.

After the liquid temperature inside the reactor had dropped to 60 ° C., an aqueous solution in which 0.4 part of Rongalite was dissolved in 10 parts of ion-exchanged water was added. Next, a mixture of 11.1 parts of acrylonitrile, 33.2 parts of styrene and 0.2 part of t-butyl hydroperoxide was added dropwise over about 1 hour for polymerization. After holding for 1 hour after the completion of dropping, an aqueous solution in which 0.0002 part of ferrous sulfate, 0.0006 part of ethylenediaminetetraacetic acid disodium salt and 0.25 part of Rongalite were dissolved in 10 parts of ion-exchanged water was added. Next, a mixture of 7.4 parts of acrylonitrile, 22.2 parts of styrene and 0.1 part of t-butyl hydroperoxide was added dropwise over about 40 minutes for polymerization. After the completion of dropping, the mixture was held for 1 hour and then cooled to obtain an aqueous dispersion of a graft copolymer (M-1D). Next, 150 parts of an aqueous solution in which calcium acetate was dissolved at a rate of 5% was heated to 60 ° C. and stirred. 100 parts of an aqueous dispersion of the graft copolymer (M-1) was gradually dropped into the aqueous calcium acetate solution to solidify. The obtained coagulum was separated, washed, and dried to obtain a dry powder of the graft copolymer (M-1D).

(Preparation of graft copolymer (M-2D))
In a reactor equipped with a reagent injection vessel, a condenser, a jacket heater and a stirrer, 119.5 parts of an aqueous dispersion of polyorganosiloxane (La-2D) and 0.94 parts of sodium polyoxyethylene alkylphenyl ether sulfate Was added, and 203 parts of ion-exchanged water was added and mixed. Thereafter, a mixture consisting of 53.2 parts of n-butyl acrylate, 0.21 part of allyl methacrylate, 0.11 part of 1,3-butylene glycol dimethacrylate and 0.13 part of t-butyl hydroperoxide was added. The atmosphere was purged with nitrogen by passing a nitrogen stream through the reactor, and the temperature was raised to 60 ° C. When the temperature inside the reactor reached 60 ° C., 0.0001 part of ferrous sulfate, 0.0003 part of ethylenediaminetetraacetic acid disodium salt and 0.24 part of Rongalite were dissolved in 10 parts of ion-exchanged water. An aqueous solution was added to initiate radical polymerization. The liquid temperature rose to 78 ° C. by polymerization of the (meth) acrylic acid ester component. This state was maintained for 1 hour to complete the polymerization of the (meth) acrylic acid ester component to obtain an aqueous dispersion of a composite rubber-like polymer (L1-2D). The volume average particle diameter of the composite rubber-like polymer (L1-2D) dispersed in the aqueous dispersion was 0.037 μm.

After the liquid temperature inside the reactor had dropped to 60 ° C., an aqueous solution in which 0.4 part of Rongalite was dissolved in 10 parts of ion-exchanged water was added. Next, a mixture of 11.1 parts of acrylonitrile, 33.2 parts of styrene and 0.2 part of t-butyl hydroperoxide was added dropwise over about 1 hour for polymerization. After holding for 1 hour after the completion of dropping, an aqueous solution in which 0.0002 part of ferrous sulfate, 0.0006 part of ethylenediaminetetraacetic acid disodium salt and 0.25 part of Rongalite were dissolved in 10 parts of ion-exchanged water was added. Next, a mixture of 7.4 parts of acrylonitrile, 22.2 parts of styrene and 0.1 part of t-butyl hydroperoxide was added dropwise over about 40 minutes for polymerization. After the completion of dropping, the mixture was kept for 1 hour and then cooled to obtain an aqueous dispersion of a graft copolymer (M-2D). Next, 150 parts of an aqueous solution in which calcium acetate was dissolved at a rate of 5% was heated to 60 ° C. and stirred. 100 parts of an aqueous dispersion of the graft copolymer (M-2D) was gradually dropped into the aqueous calcium acetate solution to solidify. The obtained coagulated product was separated, washed, and dried to obtain a dry powder of the graft copolymer (M-2D).

(Preparation of graft copolymer (M-3D))
In a reactor equipped with a reagent injection vessel, a condenser, a jacket heater and a stirrer, 119.5 parts of an aqueous dispersion of polyorganosiloxane (La-2D), 0.9 parts of polyoxyethylene alkylphenyl ether sodium sulfate Was added, and 203 parts of ion-exchanged water was added and mixed. Thereafter, a mixture consisting of 53.2 parts of n-butyl acrylate, 0.21 part of allyl methacrylate, 0.11 part of 1,3-butylene glycol dimethacrylate and 0.13 part of t-butyl hydroperoxide was added. The atmosphere was purged with nitrogen by passing a nitrogen stream through the reactor, and the temperature was raised to 60 ° C. When the temperature inside the reactor reached 60 ° C., 0.0001 part of ferrous sulfate, 0.0003 part of ethylenediaminetetraacetic acid disodium salt and 0.24 part of Rongalite were dissolved in 10 parts of ion-exchanged water. An aqueous solution was added to initiate radical polymerization. The liquid temperature rose to 78 ° C. by polymerization of the (meth) acrylic acid ester component. This state was maintained for 1 hour to complete the polymerization of the (meth) acrylic acid ester component to obtain an aqueous dispersion of a composite rubber-like polymer (L1-3D). The volume average particle diameter of the composite rubber-like polymer (L1-3D) dispersed in the aqueous dispersion was 0.05 μm.

After the liquid temperature inside the reactor had dropped to 60 ° C., an aqueous solution in which 0.4 part of Rongalite was dissolved in 10 parts of ion-exchanged water was added. Next, a mixture of 11.1 parts of acrylonitrile, 33.2 parts of styrene and 0.2 part of t-butyl hydroperoxide was added dropwise over about 1 hour for polymerization. After holding for 1 hour after the completion of dropping, an aqueous solution in which 0.0002 part of ferrous sulfate, 0.0006 part of ethylenediaminetetraacetic acid disodium salt and 0.25 part of Rongalite were dissolved in 10 parts of ion-exchanged water was added. Next, a mixture of 7.4 parts of acrylonitrile, 22.2 parts of styrene and 0.1 part of t-butyl hydroperoxide was added dropwise over about 40 minutes for polymerization. After the completion of dropping, the mixture was kept for 1 hour and then cooled to obtain an aqueous dispersion of a graft copolymer (M-3D). Next, 150 parts of an aqueous solution in which calcium acetate was dissolved at a rate of 5% was heated to 60 ° C. and stirred. 100 parts of an aqueous dispersion of the graft copolymer (M-3D) was gradually dropped into the aqueous calcium acetate solution to solidify. The obtained coagulated product was separated, washed, and dried to obtain a dry powder of the graft copolymer (M-3D).

(Preparation of graft copolymer (M-4D))
In a reactor equipped with a reagent injection container, a condenser, a jacket heater and a stirrer, 119.5 parts of an aqueous dispersion of polyorganosiloxane (La-1D) and 0.51 part of sodium polyoxyethylene alkylphenyl ether sulfate Was added, and 203 parts of ion-exchanged water was added and mixed. Thereafter, a mixture consisting of 53.2 parts of n-butyl acrylate, 0.21 part of allyl methacrylate, 0.11 part of 1,3-butylene glycol dimethacrylate and 0.13 part of t-butyl hydroperoxide was added. The atmosphere was purged with nitrogen by passing a nitrogen stream through the reactor, and the temperature was raised to 60 ° C. When the temperature inside the reactor reached 60 ° C., 0.0001 part of ferrous sulfate, 0.0003 part of ethylenediaminetetraacetic acid disodium salt and 0.24 part of Rongalite were dissolved in 10 parts of ion-exchanged water. An aqueous solution was added to initiate radical polymerization. The liquid temperature rose to 78 ° C. by polymerization of the (meth) acrylic acid ester component. This state was maintained for 1 hour to complete the polymerization of the (meth) acrylic acid ester component to obtain an aqueous dispersion of a composite rubber-like polymer (L1-4D). The volume average particle diameter of the composite rubber-like polymer (L1-4D) dispersed in the aqueous dispersion was 0.18 μm.

After the liquid temperature inside the reactor had dropped to 60 ° C., an aqueous solution in which 0.4 part of Rongalite was dissolved in 10 parts of ion-exchanged water was added. Next, a mixture of 11.1 parts of acrylonitrile, 33.2 parts of styrene and 0.2 part of t-butyl hydroperoxide was added dropwise over about 1 hour for polymerization. After holding for 1 hour after the completion of dropping, an aqueous solution in which 0.0002 part of ferrous sulfate, 0.0006 part of ethylenediaminetetraacetic acid disodium salt and 0.25 part of Rongalite were dissolved in 10 parts of ion-exchanged water was added. Next, a mixture of 7.4 parts of acrylonitrile, 22.2 parts of styrene and 0.1 part of t-butyl hydroperoxide was added dropwise over about 40 minutes for polymerization. After the completion of dropping, the mixture was kept for 1 hour and then cooled to obtain an aqueous dispersion of a graft copolymer (M-4D). Next, 150 parts of an aqueous solution in which calcium acetate was dissolved at a rate of 5% was heated to 60 ° C. and stirred. 100 parts of an aqueous dispersion of the graft copolymer (M-4D) was gradually dropped into the calcium acetate aqueous solution to be solidified. The obtained coagulated product was separated, washed, and dried to obtain a dry powder of the graft copolymer (M-4D).

(Preparation of graft copolymer (M-5D))
In a reactor equipped with a reagent injection container, a condenser, a jacket heater and a stirrer, 119.5 parts of an aqueous dispersion of polyorganosiloxane (La-1D) and 0.33 parts of sodium polyoxyethylene alkylphenyl ether sulfate Was added, and 203 parts of ion-exchanged water was added and mixed. Thereafter, a mixture consisting of 53.2 parts of n-butyl acrylate, 0.21 part of allyl methacrylate, 0.11 part of 1,3-butylene glycol dimethacrylate and 0.13 part of t-butyl hydroperoxide was added. The atmosphere was purged with nitrogen by passing a nitrogen stream through the reactor, and the temperature was raised to 60 ° C. When the temperature inside the reactor reached 60 ° C., 0.0001 part of ferrous sulfate, 0.0003 part of ethylenediaminetetraacetic acid disodium salt and 0.24 part of Rongalite were dissolved in 10 parts of ion-exchanged water. An aqueous solution was added to initiate radical polymerization. The liquid temperature rose to 78 ° C. by polymerization of the (meth) acrylic acid ester component. This state was maintained for 1 hour to complete the polymerization of the (meth) acrylic acid ester component to obtain an aqueous dispersion of a composite rubber-like polymer (L1-5D). The volume average particle diameter of the composite rubber-like polymer (L1-5D) dispersed in the aqueous dispersion was 0.24 μm.

After the liquid temperature inside the reactor had dropped to 60 ° C., an aqueous solution in which 0.4 part of Rongalite was dissolved in 10 parts of ion-exchanged water was added. Next, a mixture of 11.1 parts of acrylonitrile, 33.2 parts of styrene and 0.2 part of t-butyl hydroperoxide was added dropwise over about 1 hour for polymerization. After holding for 1 hour after the completion of dropping, an aqueous solution in which 0.0002 part of ferrous sulfate, 0.0006 part of ethylenediaminetetraacetic acid disodium salt and 0.25 part of Rongalite were dissolved in 10 parts of ion-exchanged water was added. Next, a mixture of 7.4 parts of acrylonitrile, 22.2 parts of styrene and 0.1 part of t-butyl hydroperoxide was added dropwise over about 40 minutes for polymerization. After the completion of dropping, the mixture was kept for 1 hour and then cooled to obtain an aqueous dispersion of a graft copolymer (M-5D). Next, 150 parts of an aqueous solution in which calcium acetate was dissolved at a rate of 5% was heated to 60 ° C. and stirred. 100 parts of an aqueous dispersion of the graft copolymer (M-5D) was gradually dropped into the calcium acetate aqueous solution to solidify. The obtained coagulated product was separated, washed, and dried to obtain a dry powder of graft copolymer (M-5D).

<Methacrylate ester resin (G)>
(Preparation of methacrylate ester resin (G-1D))
In a stainless steel polymerization tank equipped with a stirrer, 150 parts of ion exchange water, 99 parts of methyl methacrylate, 1 part of methyl acrylate, 0.2 part of 2,2′-azobis (isobutyronitrile), 0.25 part of n-octyl mercaptan , 0.47 part of calcium hydroxyapatite and 0.003 part of potassium alkenyl succinate were charged. The internal temperature of the polymerization tank was set to 75 ° C. for 3 hours, and the temperature was raised to 90 ° C. for 1 hour. The contents were extracted, washed with a centrifugal dehydrator, and dried to obtain a powdery methacrylate resin (G-1D). The monomers are shown in Table 21D.

(Preparation of methacrylate ester resin (G-2D))
In a stainless polymerization tank equipped with a stirrer, 150 parts of ion exchange water, 82 parts of methyl methacrylate, 12 parts of N-phenylmaleimide, 6 parts of styrene, 0.2 part of 2,2′-azobis (isobutyronitrile), n-octyl Mercaptan (0.25 part) and polyvinyl alcohol (0.7 part) were charged. The internal temperature of the polymerization tank was set at 75 ° C. for 3 hours, and the temperature was raised to 90 ° C. for 1 hour. The contents were extracted, washed with a centrifugal dehydrator, and dried to obtain a powdery methacrylic ester resin (G-2D). The monomers are shown in Table 21D.

(Preparation of methacrylate ester resins (G-3D) to (G-11D))
As shown in Table 21D and Table 22D, except that the type of the vinyl monomer mixture (m3) was changed, in the same manner as the methacrylate ester resin (G-2D), the methacrylate ester resin (G-3D) to (G-11D) was obtained.

<Styrene copolymer (H)>
(Preparation of styrene copolymer (H-1D))
In a stainless steel polymerization tank equipped with a stirrer substituted with nitrogen, 120 parts of ion exchange water, 0.1 part of polyvinyl alcohol, 0.3 part of 2,2′-azobis (isobutyronitrile), 25 parts of acrylonitrile, 75 parts of styrene, t -0.35 part of dodecyl mercaptan was charged and reacted at an initial temperature of 60 ° C for 5 hours. The temperature was raised to 120 ° C. and reacted for 4 hours. The contents were taken out to obtain a styrene copolymer (H-1D).

(Preparation of styrene copolymer (H-2D))
In a stainless steel polymerization tank equipped with a stirrer, 150 parts of ion exchange water, 7 parts of methyl methacrylate, 23 parts of acrylonitrile, 70 parts of styrene, 0.2 part of 2,2′-azobis (isobutyronitrile), n-octyl mercaptan 0 .25 parts, calcium hydroxyapatite 0.47 part, and potassium alkenyl succinate 0.003 part were charged, the internal temperature was raised to 75 ° C., and the reaction was performed for 3 hours. The reaction was completed by raising the temperature to 90 ° C. and holding for 60 minutes. The contents were taken out, repeatedly washed with a centrifugal dehydrator, dehydrated, and dried to obtain a styrene copolymer (H-2D).

(Preparation of styrenic copolymers (H-3D) to (H-5D))
As shown in Table 23D, except that the amount of the vinyl monomer mixture (m4) was changed, in the same manner as the styrene copolymer (H-2D), the styrene copolymer (H-3D) to ( H-5D) was obtained.

[Example 1D]
10 parts of graft copolymer (D-1D), 14 parts of graft copolymer (M-1D) and 76 parts of methacrylic ester resin (G-1D) were mixed and a twin screw extruder equipped with a 30 mmφ vacuum vent (Ikekai A thermoplastic resin composition was prepared by melt-kneading at 240 ° C. and 93.325 kPa vacuum using a “PCM30” manufactured by the company. The MVR of the thermoplastic resin composition is shown in Table 24D.
The thermoplastic resin composition was pelletized, and various molded articles were molded, and impact resistance, color development, scratch resistance, scratch resistance, heat resistance, and lubricity (squeak noise) were evaluated. The results are shown in Table 24D.

[Examples 2D to 88D]
A thermoplastic resin composition was prepared and MVR was measured in the same manner as in Example 1D, except that the formulation shown in Tables 24D to 32D was changed.
The thermoplastic resin composition was pelletized, and various molded articles were molded, and impact resistance, color development, scratch resistance, scratch resistance, heat resistance, and lubricity (squeak noise) were evaluated. The results are shown in Tables 24D to 32D.

[Comparative Examples 1D to 24D]
A thermoplastic resin composition was prepared and MVR was measured in the same manner as in Example 1D, except that the formulation shown in Table 33D to Table 35D was changed.
The thermoplastic resin composition was pelletized, and various molded articles were molded, and impact resistance, color development, scratch resistance, scratch resistance, heat resistance, and lubricity (squeak noise) were evaluated. The results are shown in Table 33D to Table 35D.

The thermoplastic resin compositions of Examples 1D to 88D were excellent in fluidity. In addition, the molded products obtained in Examples 1D to 88D were excellent in lubricity (squeaking noise), impact resistance, heat resistance, color development, scratch resistance, and scratch resistance.
Therefore, the thermoplastic resin composition according to the fifth aspect of the present invention has excellent fluidity. When the thermoplastic resin composition according to the fifth aspect of the present invention is used, lubricity (squeak noise) and impact resistance are achieved. It can be seen that a molded product having excellent properties, color developability, scratch resistance and scratch resistance can be obtained, and can be applied to uses such as vehicle interior / exterior parts, vehicle exterior parts, office equipment, home appliances, and building materials.

On the other hand, from the results of Comparative Examples 1D to 24D, those other than the present invention could not obtain lubricity (squeak noise) characteristics, and the molded article had low impact resistance and scratch resistance.

The molded article using the thermoplastic resin composition of the present invention is useful as vehicle interior parts, vehicle exterior parts, office equipment, home appliances, building materials, and the like.

10 jig 11 tip 12 laminated sheet 13 molded product (Ma) 21 test piece 21a rib structure 22 test piece

Claims

The weight average molecular weight (Mw) is 17 × 10 4 to 35 × 10 4 , and the molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 1 to 3 In the presence of the ethylene / α-olefin copolymer (A) or the crosslinked ethylene / α-olefin copolymer (C) obtained by crosslinking the ethylene / α-olefin copolymer (A). A graft copolymer obtained by polymerizing a vinyl monomer mixture (m1) containing a compound and a vinyl cyanide compound.
Graft copolymer in which the gel content of the crosslinked ethylene / α-olefin copolymer (C) is 35 to 75% by mass with respect to the total mass of the crosslinked ethylene / α-olefin copolymer (C). .
The graft copolymer according to claim 1 or 2, wherein the ethylene / α-olefin copolymer (A) is an ethylene / propylene copolymer.
The ethylene unit content of the ethylene / α-olefin copolymer (A) is 45 to 65% by mass based on the total mass of the structural units constituting the ethylene / α-olefin copolymer (A). The graft copolymer according to any one of claims 1 to 3, wherein
The graft copolymer according to any one of claims 1 to 4, wherein the polymerization is emulsion polymerization.
A thermoplastic resin composition comprising the graft copolymer (D) according to any one of claims 1 to 5 and a hard component (J).
The thermoplastic resin composition according to claim 6, wherein the hard component (J) is a styrene-based copolymer (H).
The graft copolymer (D) according to any one of claims 1 to 5,
A thermoplastic resin composition comprising: a methacrylic ester resin (G) obtained by polymerizing a vinyl monomer mixture (m3) containing a methacrylic ester.
The graft copolymer (D) according to any one of claims 1 to 5,
A graft copolymer (F) obtained by polymerizing a vinyl monomer mixture (m2) containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of the crosslinked acrylic ester rubber polymer (E). )When,
A methacrylic acid ester resin (G) obtained by polymerizing a vinyl monomer mixture (m3) containing a methacrylic acid ester,
The volume average particle diameter of the ethylene / α-olefin copolymer (A) or the crosslinked ethylene / α-olefin copolymer (C) contained in the graft copolymer (D) in the thermoplastic resin composition is 0.00. 2 μm to 0.6 μm,
The volume average particle diameter of the crosslinked acrylic ester rubber-like polymer (E) contained in the graft copolymer (F) in the thermoplastic resin composition is 0.05 μm to 0.18 μm,
Of the total (100% by mass) of the ethylene / α-olefin copolymer (A), the cross-linked ethylene / α-olefin copolymer (C), and the cross-linked acrylate rubber polymer (E), ethylene / α The proportion of the olefin copolymer (A) or the crosslinked ethylene / α-olefin copolymer (C) is 15 to 85% by mass, and the proportion of the crosslinked acrylate rubber polymer (E) is 85 A thermoplastic resin composition having a content of 15% by mass.
The graft copolymer (D) according to any one of claims 1 to 5,
A graft copolymer (M) obtained by polymerizing a vinyl monomer mixture (m5) in the presence of a composite rubber-like polymer (L) containing a polyorganosiloxane (La);
A methacrylic acid ester resin (G) obtained by polymerizing a vinyl monomer mixture (m3) containing a methacrylic acid ester,
The volume average particle diameter of the ethylene / α-olefin copolymer (A) or the crosslinked ethylene / α-olefin copolymer (C) contained in the graft copolymer (D) in the thermoplastic resin composition is 0.00. 2 μm to 0.6 μm,
The volume average particle size of the composite rubber-like polymer (L) contained in the graft copolymer (M) in the thermoplastic resin composition is 0.05 μm to 0.18 μm,
Of the total (100% by mass) of ethylene / α-olefin copolymer (A), crosslinked ethylene / α-olefin copolymer (C) and composite rubber-like polymer (L), ethylene / α-olefin copolymer The ratio of the polymer (A) or the crosslinked ethylene / α-olefin copolymer (C) is 15 to 85% by mass, and the ratio of the composite rubbery polymer (L) is 85 to 15% by mass. Plastic resin composition.
The graft copolymer (M) is a unit derived from a polyorganosiloxane (La) or (meth) acrylic acid ester, a unit derived from a crosslinking agent, or a unit derived from a graft crossing agent, or both In the presence of the composite rubber-like polymer (L1) comprising the poly (meth) acrylic acid ester (Lb) having a vinyl monomer component (m5) containing an aromatic vinyl compound and a vinyl cyanide compound. The thermoplastic resin composition according to claim 10, which is obtained in the above manner.
A molded article formed from the thermoplastic resin composition according to any one of claims 6 to 11.